compound and use of that compound

专利摘要:
OXO-TUNGSTEN-ALKYLIDIDE COMPLEXES FOR Z-SELECTIVE OLEPHINE METATHESIS. The present application describes oxotungsten-alkylidene complexes for olefin metathesis.
公开号:BR112014010951B1
申请号:R112014010951-6
申请日:2012-11-07
公开日:2020-12-08
发明作者:Richard Royce Schrock；Dmitry Vyacheslavovich Peryshkov；Amir H. Hoveyda
申请人:Trustees Of Boston College；Massachusetts Institute Of Technology；
IPC主号:

专利说明:

CROSS REFERENCE WITH RELATED REQUESTS
[001] The present invention claims priority for Provisional U.S. Order Serial No. 61 / 556,643, filed on November 7, 2011, the entire amount of which is hereby incorporated by reference. DECLARATION REGARDING FEDERAL FUNDING RESEARCH OR DEVELOPMENT
[002] This invention was made with government support under Concession No. DE-FG02-86ER13564 granted by “U.S. DEPARTMENT OF ENERGY” and under Concession No. CHE-1111133 granted by “THE NATIONAL SCIENCE FOUNDATION”. The government has some rights to this invention. FIELD OF THE INVENTION
[003] The present invention is generally related to olefin metathesis catalyst precursors. BACKGROUND OF THE INVENTION
[004] The catalytic olefin metathesis transformed chemical synthesis and offers exceptionally efficient pathways for the synthesis of alkenes. A large number of commercially important molecules contain olefins. These chemical specialties include biologically active molecules, oleochemicals, renewables, fine chemicals and polymeric materials, to name just a few. In addition, many reactions in organic chemistry require alkenes as starting materials. Consequently, there remains an unmet need for improved methods and catalysts for the metathesis reaction. BRIEF DESCRIPTION OF THE DRAWINGS
[005] Figure 1. Drawing of I-1 thermal ellipsoid.
[006] Figure 2. Design of thermal ellipsoid (50% probability) of sin-W (O) (CH-t-Bu) (OHIPT) (Me2Pir) (I-2). Hydrogen atoms have been omitted for clarity. Distances (A) and selected connection angles (°): W1-C1 = 1,886 (3), W1-O2 = 1,695 (3), W1-O1 = 1,868 (2), W1-N1 = 2,001 (2), W1 -O1-C21 = 166.9 (2), W1-C1-C2 = 136.7 (3).
[007] Figure 3. Design of thermal ellipsoid (50% probability) of sin-W (O) (CH-t-Bu) (OHMT) (Me2Pir) (PMe2Ph) (I-4). Hydrogen atoms have been omitted for clarity. Solvent molecules are not shown. Distances (A) and selected connection angles (°): W1-C1 = 1,900 (3), W1-O2 = 1,717 (2), W1-O1 = 1,964 (2), W1-N1 = 2,074 (2), W1 -P1 = 2.580 (1), W1-O1-C21 = 159.8 (2), W1-C1-C2 = 141.0 (2).
[008] Figure 4. The 1H-NMR spectrum typical of the product of the 1-octene homo-coupling mixture. Olefinic region of 1H-NMR spectrum (in CDCl3) of a crude product of the 1-octene homo-coupling promoted by I-4. No trans products (at approximately 5.38 ppm) can be observed. The asterisk represents residual ethylene.
[009] Figure 5. Design of thermal ellipsoid (50% probability) of W (O) (B (C6F5) 3) (CH-t-Bu) (OHMT) (Me2Pir) (I-6). Hydrogen atoms have been omitted for clarity. Distances (A) and selected connection angles (°): W1-C1 = 1,868 (2), W1-O2 = 1,759 (2), W1-O1 = 1,860 (2), W1-N1 = 1,968 (2), B1 -O2 = 1,571 (3), W1-O1-C21 = 150.9 (1), W1-C1-C2 = 155.4 (2).
[010] Figure 6. Spectra of 1H-NMR of WO (CH-t-Bu) (Me2Pir) (HYPTO) solution in C6D6 after addition of 1 ethylene atmosphere. Signs assigned to the proposed substituted and unsubstituted metallacycles are marked * and #, respectively.
[011] Figure 7. Variable temperature spectra of 1H-NMR of I-2 and of the mixture of I-2 and B (C6F5) 3.
[012] Figure 8. Graph of thermal ellipsoid (50% probability) of W (O) (CH-t-Bu) (Ph2Pir) (OHMT). Hydrogen atoms have been omitted for clarity. Distances (A) and selected connection angles (deg): W1- C1 = 1,895 (2), W1-O1 = 1,690 (1), W1-O2 = 1,894 (1), W1-N1 = 2,037 (2); W1-C1-C2 = 141.1 (1), W1-O2-C6 = 143.1 (1).
[013] Figure 9. Graph of thermal ellipsoid (50% probability) of W (O) (CH-t-Bu) [N (C6F5) 2] (OHMT) (PMe2Ph). Hydrogen atoms have been omitted for clarity. Distances (A) and selected connection angles (deg): W1-C1 = 1,898 (2), W1-O1 = 1,710 (2), W1- O2 = 1,965 (1), W1-N1 = 2,127 (2), W1 -P1 = 2.564 (1), W1-C1-C2 = 141 (2), W1-O2-C6 = 154.0 (1).
[014] Figure 10. Graph of thermal ellipsoid (50% probability) of W (O) (C3H6) (OHMT) pyramidal square (Silox). Hydrogen atoms, except those in the metalacycle, have been omitted for clarity. Only the main disturbance component is shown. Distances (A) and selected connection angles (deg): W1-C1 = 2,172 (3), W1-C3 = 2,168 (3), W1-O1 = 1,690 (2), W1-O2 = 1,896 (2), W1 -O3 = 1.875 (3), C1-C2 = 1.527 (4), C2-C3 = 1.522 (4); W1-C1-C2 = 95.0 (2), W1-C3-C2 = 95.4 (2), C1-C2-C3 = 95.6 (2), C1-W1-C3 = 62.7 (1 ), O2-W1-O3 = 103.3 (1), O1-W1- O2 = 113.6 (1), O1-W1-O3 = 113.4 (1), W1-O2-C4 = 148.0 (1), W1-O3-Sil = 161.9 (4).
[015] Figure 11. Graph of thermal ellipsoid (50% probability) of tetrahedral W (O) (CH2) (OHMT) 2. Hydrogen atoms, except for those in methylidene, have been omitted for clarity. Only the main disturbance component is shown. Distances (A) and selected connection angles (deg): W1-C1 = 1,895 (8), W1-O1 = 1,694 (5), W1- O2 = 1,881 (2), W1-O3 = 1,917 (2); W1-C1-H1A = 109 (3), W1-C1- H1B = 127 (3), H1A-C1-H1B = 123 (4), O1-W1-C1 = 103.1 (3), W1- O2- C2 = 136.3 (2), W1-O3-C26 = 138.6 (2). DETAILED DESCRIPTION OF CERTAIN MODALITIES 1. General description of certain embodiments of the invention
[016] At the beginning of the development of tungsten-containing olefin metathesis catalysts, it was demonstrated that more metathesis-active and reproducible systems were produced when oxo-tungsten complexes were deliberately employed or were present as impurities in WCl6 (KJ Ivin and JC Mol, "Olefin Metathesis and Metathesis Polymerization"; Academic Press: San Diego, 1997; KJ Ivin, "Olefin Metathesis"; Academic Press, 1983; Calderon, N .; Ofstead, EA; Ward, JP; Judy, WA; Scott, KWJ Am. Chem. Soc. 1968, 90, 4,133; Basset, JM; Coudurier, G .; Praliaud, HJ Catal. 1974, 34, 152; Mocella, MT; Rovner, R .; Muetterties, ELJ Am. Chem 1976, 98, 4,689; Burwell, RL, Jr .; Brenner, AJ Mol. Catal. 1976, 1, 77; Kress, JRM; Russell, MJM; Wesolek, MG; Osborn, JAJ Chem. Soc. Chem. Comm. 1980, 431; Muetterties, EL; Band, E. 1980, 102, 6572; Kress, JRM; Wesolek, MG; Le Ny; J. -P .; Osborn, JAJ Chem. Soc. Chem. Comm. 1981, 1039; Kress, JRM; Wesolek, MG; Osborn, JAJ Chem. S Chem. Comm. 1982, 514; Kress, JRM; Osborn, JAJ Am. Chem. Soc. 1983, 105, 6,346). The possibility that oxo-alkylidene complexes, for example, W (O) (CHR) X2 (where X is a chloride, alkoxide etc.) are the true catalysts in at least some of the "classic" olefin metathesis systems became more likely when 1 (L = PMe3 and other phosphines) was prepared and isolated in good yield (Schrock, RR; Rocklage, SM; Wengrovius, J. FL; Rupprecht, G .; Fellmann, JJ Molec. Catal. 1980, 8, 73; Wengrovius, J. FL; Schrock, RR; Churchill, MR; Missert, JR; Youngs, WJJ Am. Chem. Soc. 1980, 102, 4.515; Wengrovius, J. FL; Schrock, RR Organometallics 1982, 1 , 148). Compound 1 was the first tungsten-alkylidene complex with a high oxidation state that would both (i) metastasize terminal and internal olefins (in the presence of a trace of AlCl3) and (ii) produce a new alkylidene that could be observed as a consequence of olefin metathesis. The three most likely possibilities for the role of AlCl3 are halide removal to generate monocatonic or dicatonic species, removal of a phosphine to generate the 16 electron monophosphine adduct (Wengrovius, J. FL; Schrock, RR; Churchill, MR; Missert , JR; Youngs, WJJ Am. Chem. Soc. 1980, 102, 4,515), or activation by adding AlCl3 to the oxo ligand (Schrock, RR; Rocklage, SM; Wengrovius, J. FL; Rupprecht, G .; Fellmann, JJ Molec. Catal. 1980, 8, 73; Wengrovius, J. FL; Schrock, RR; Churchill, MR; Missert, JR; Youngs, WJJ Am. Chem. Soc. 1980, 102, 4.515; Wengrovius, J. FL; Schrock, RR Organometallics 1982, 1, 148).

[017] At the time 1 was discovered, tantalum-alkylidene complexes became functional olefin metathesis catalysts through the use of alkoxides as binders (Rocklage, SM; Fellmann, JD; Rupprecht, GA; Messerle, LW; Schrock , RRJ Am. Chem. Soc. 1981, 103, 1,440; Schrock, RR Polyhedron 1995, 14, 3,177). Therefore, some attempts were made to prepare a species of W (O) (CH-t-Bu) (OR) 2 from 1, but none of these species has been isolated and characterized. Due to the synthetic problems encountered with the attempted alkylation of oxo complexes, including the removal of the oxo binder entirely (Kress, JRM; Wesolek, MG; Osborn, JAJ Chem. Soc. Chem. Comm. 1982, 514; Kress, JRM; Osborn, JAJ Am. Chem. Soc. 1983, 105, 6,346), and to protect alkylidenes from bimolecular decomposition, attention has been paid to the synthesis of W and Mo imido-alkylidene complexes, especially those containing a phenylimido linker such as example, N (2,6-i-Pr2C6H3) (Schrock, RR Chem. Rev. 2002, 102, 145-180; Schrock, RR in Braterman, PR, Ed. “Reactions of Coordinated Ligands”, Plenum: New York, 1986, page 221). Due to the success of imidoalkylidene complexes in olefin metathesis, interest in oxoalkylidene complexes in the past 25 years has been small (Bryan, JC; Mayer, JCJ Am. Chem. Soc. 1990, 112, 2,298; Blosch, LL; Abboud, K .; Boncella, JMJ Am. Chem. Soc. 1991, 113, 7,066; Ahn, S .; Mayr, AJ Am. Chem. Soc. 1996, 118, 7,408; De la Mata, FJ; Grubbs, RH Organometallics 1996, 15, 577; O'Donoghue, MB; Schrock, RR; LaPointe, AM; Davis. WM Organometallics 1996, 15, 1,334; Crane, TW; White, PS; Templeton, JL Organometallics 1999, 18, 1,897).
[018] The most recent developments in the chemistry of Mo and W imidoalkylidene have been monopyrride monoaryloxide (MAP) complexes (Schrock, R.R. Chem. Rev. 2009, 109, 3.211). One of the most interesting findings is the ability of some MAP catalysts to promote Z-selective metathesis reactions as a consequence of the presence of a relatively "large" and "small" imido aryloxide group (Ibrahem, I .; Yu, M .; Schrock, RR; Hoveyda, AHJ Am. Chem. Soc., 2009, 131, 3,844; Flook, MM; Jiang, AJ; Schrock, RR; Muller, P .; Hoveyda, AHJ Am. Chem. Soc. 2009, 131, 7,962; Flook, MM; Gerber, LCH; Debelouchina, GT; Schrock, RR Macromolecules 2010, 43, 7,515; Flook, MM; Ng, VWL; Schrock, RRJ Am. Chem. Soc. 2011, 133, 1,784; Jiang, AJ ; Zhao, Y .; Schrock, RR; Hoveyda, AHJ Am. Chem. Soc. 2009, 131, 16.630; Marinescu, SC; Schrock, RR; Muller, P .; Takase, MK; Hoveyda, AH Organometallics, 2011, 30 , 1,780; Marinescu, SC; Levine, DS; Zhao, Y .; Schrock, RR; Hoveyda, AHJ Am. Chem. Soc. 2011, 133, 11,512; Malcolmson, SJ; Meek, SJ; Sattely, ES; Schrock, RR ; Hoveyda, AH Nature 2008, 456, 933; Meek, SJ; O ’Brien, R.V .; Llaveria, J .; Schrock, R.R .; Hoveyda, A.H. Nature 2011, 471, 461; Yu, M .; Wang, C .; Kyle, A.F .; Jakubec, P .; Dixon, D.J .; Schrock, R.R .; Hoveyda, A.H. Nature 2011, 479, 88). The preferred metal for Z-selective coupling of terminal olefins at this point appears to be tungsten and the most successful aryloxide ligand has been O-2,6- (2,4,6-triisopropylphenyl) 2C6H3 or OHIPT. (The most active molybdenum complexes (Schrock, RR, King, AJ; Marinescu, SC; Simpson, JH; Muller, P. Organometallics 2010, 29, 5,241) appear to isomerize product Z in E.) It has been proposed that the steric demands uncommon OHIPT ligands force all metallacyclobutane substituents to one side of the metallacycle ring and therefore allow only Z products to form. Since an oxo ligand is smaller than any NR (R not H) ligand, the question arises whether MAP versions of oxo-tungsten-alkylidene complexes would be useful Z-selective catalysts.
[019] In some embodiments, the present invention provides a compound of formula I
: where: each of R1 and R2 is independently R, -OR, -SR, - N (R) 2, -OC (O) R, -SOR, -SO2R, -SO2N (R) 2, -C ( O) N (R) 2, -NRC (O) R or -NRSO2R; each R3 and R4 is halogen, R, -N (R) 2, -NRC (O) R, - NRC (O) OR, -NRC (O) N (R) 2, -NRSO2R, -NRSO2N (R) 2 , -NROR, NR3, - OR, O (R) 2, a linker containing phosphorus, or an optionally substituted group selected from a 5-6 membered heteroaryl monocyclic ring that has at least one nitrogen and 0-3 additional selected heteroatoms regardless of nitrogen, oxygen or sulfur, a 4-7 membered saturated or partially unsaturated heterocyclic ring that has at least one nitrogen and 0-2 additional heteroatoms selected independently of nitrogen, oxygen or sulfur, a saturated or partially unsaturated bicyclic heterocyclic ring 7-10 members that have at least one nitrogen and 0-4 additional heteroatoms selected independently of nitrogen, oxygen or sulfur or an 8-10 membered bicyclic heteroaryl ring that has at least one nitrogen and 0-4 additional heteroatoms selected independently of nitrogen , oxygen or sulfur; each R is independently hydrogen or an optionally substituted group selected from C1-20 aliphatic, C120 heteroaliphatic having 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, phenyl, ferrocene, a 3-7 membered saturated or partially unsaturated carbocyclic ring , an 8-10 membered saturated, partially unsaturated or aryl bicyclic ring, a 5-6 membered heteroaryl monocyclic ring that has 14 heteroatoms independently selected from nitrogen, oxygen or sulfur, a 4-7 membered saturated or partially unsaturated heterocyclic ring which has 1-3 heteroatoms selected independently of nitrogen, oxygen or sulfur, a 7-10 membered saturated or partially unsaturated bicyclic heterocyclic ring which has 1-5 heteroatoms selected independently of nitrogen, oxygen or sulfur or an 8- bicyclic heteroaryl ring 10 members that have 1-5 heteroatoms selected independently of nitrogen, oxygen or sulfur, or: two or three R groups on the same nitrogen atom are taken together with nitrogen to form an optionally substituted 3-12 membered saturated, partially unsaturated or aryl ring that has 0-5 additional hetero atoms, not including the same nitrogen atom, selected independently of nitrogen, oxygen or sulfur; or: two R groups on the same oxygen atom are taken together with oxygen to form an optionally substituted saturated, partially unsaturated or 3-12 membered aryl ring that has 0-5 additional heteroatoms, not including the same oxygen atom, independently selected from nitrogen, oxygen or sulfur; n is 0, 1 or 2; each R5 is independently a monodentate ligand, or two R5 are taken together with their intervening atoms to form an optionally substituted bidentate group; and two or more of R1, R2, R3, R4 and R5 can be taken together with their intervening atoms to form an optionally substituted polyidentated ligand.
[020] Additional aspects of compounds of formula I are described in detail, below. 2. Definitions
[021] Compounds of the present invention include those described herein generally, and are further illustrated by the classes, subclasses and species disclosed herein. As used herein, the following definitions should apply, unless otherwise indicated. For the purposes of this invention, chemical elements are identified according to the Periodic Table of Elements, CAS version, “Handbook of Chemistry and Physics”, 75th Edition. In addition, general principles of organic chemistry are described in “Organic Chemistry”, Thomas Sorrell, University Science Books, Sausalito: 1999, and “March's Advanced Organic Chemistry”, 5th Edition, Ed .: Smith, MB and March, J., John Wiley & Sons, New York: 2001, whose total contents are incorporated by reference.
[022] The term "aliphatic" or "aliphatic group", as used herein, means a straight-chain (ie, unbranched) or branched, substituted or unsubstituted hydrocarbon chain, which is completely saturated or contains one or more unsaturation units, or a monocyclic hydrocarbon, bicyclic hydrocarbon or tricyclic hydrocarbon that is completely saturated or that contains one or more unsaturation units, but which is not aromatic (also here called "carbocycle", "cycloaliphatic" or "cycloalkyl"), that has a single point of adhesion to the rest of the molecule. Unless otherwise specified, aliphatic groups contain 1-30 aliphatic carbon atoms. In some embodiments, aliphatic groups contain 1-20 aliphatic carbon atoms. In other embodiments, aliphatic groups contain 1-10 aliphatic carbon atoms. In yet other embodiments, aliphatic groups contain 1-5 aliphatic carbon atoms and, in still other embodiments, aliphatic groups contain 1, 2, 3 or 4 aliphatic carbon atoms. Suitable aliphatic groups include, without limitation, alkyl, alkenyl, straight or branched, substituted or unsubstituted, and such hybrids such as (cycloalkyl) alkyl, (cycloalkenyl) alkyl or (cycloalkyl) alkenyl.
[023] The term "cycloaliphatic", as used herein, refers to saturated or partially unsaturated monocyclic, bicyclic or polycyclic ring systems, as described herein, which have 3 to 14 members, in which the aliphatic ring system is optionally substituted as defined above and described here. Cycloaliphatic groups include, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cycloheptenyl, cyclooctyl, cyclooctenyl, norbornil, adamantyl, and cyclooctadienyl. In some embodiments, cycloalkyl has 3-6 carbons. The term "cycloaliphatic" can also include aliphatic rings that are fused to one or more aromatic or non-aromatic rings, for example, decahydronafty or tetrahydronaphile, where the radical or point of adhesion is on the aliphatic ring. In some embodiments, a carbocyclic group is bicyclic. In some embodiments, a carbocyclic group is tricyclic. In some embodiments, a carbocyclic group is polycyclic. In some embodiments, “cycloaliphatic” (or “carbocycle” or “cycloalkyl”) refers to a C3-C6 monocyclic hydrocarbon, or a C8-C10 bicyclic hydrocarbon that is completely saturated or that contains one or more units of unsaturation, but which is not aromatic, which has a single point of adhesion to the rest of the molecule, or the C9-C16 tricyclic hydrocarbon which is completely saturated or which contains one or more units of unsaturation, but which is not aromatic, which has a single point of adhesion to the rest of the molecule.
[024] As used herein, the term "alkyl" receives its common meaning in the art may include saturated aliphatic groups, including straight chain alkyl groups, branched chain alkyl groups, cycloalkyl (alicyclic) groups, cycloalkyl groups substituted with alkyl and groups alkyl substituted with cycloalkyl. In certain embodiments, a straight chain or branched chain alkyl has about 1-20 carbon atoms in its framework (for example, C1-C20 for straight chain, C2-C20 for branched chain) and, alternatively, about 110. In some embodiments, a cycloalkyl ring has about 3-10 carbon atoms in its ring structure, where these rings are monocyclic or bicyclic and, alternatively, about 5, 6 or 7 carbons in the ring structure . In some embodiments, an alkyl group may be a lower alkyl group, wherein a lower alkyl group comprises 1-4 carbon atoms (for example, C1-C4 for straight chain lower alkyl).
[025] As used herein, the term "alkenyl" refers to an alkyl group, as defined herein, which has one or more double bonds.
[026] As used herein, the term "alkynyl" refers to an alkyl group, as defined herein, which has one or more triple bonds.
[027] The term "heteroalkyl" receives its common meaning in the art and refers to alkyl groups as described herein, in which one or more carbon atoms are replaced with a heteroatom (for example, oxygen, nitrogen, sulfur, and the like) . Examples of heteroalkyl groups include, without limitation, alkoxy, poly (ethylene glycol) -, alkyl-substituted amino, tetrahydrofuranyl, piperidinyl, morpholinyl, etc.
[028] The term "aryl", used alone or as part of a larger portion as in "aralkyl", "aralkoxy" or "aryloxy alkyl", refers to monocyclic or bicyclic ring systems that have a total of five to fourteen ring members, where at least one ring in the system is aromatic and where each ring in the system contains 3 to 7 ring members. The term "aryl" can be used interchangeably with the term "aryl ring". In certain embodiments of the present invention, "aryl" refers to an aromatic ring system that includes, without limitation, phenyl, biphenyl, naphthyl, binafty, anthracyl and the like, which may harbor one or more substituents. Also included within the scope of the term "aryl", as used herein, is a group in which an aromatic ring is fused to one or more non-aromatic rings, for example, indanyl, phthalimidyl, naphthymidyl, phenanthridinyl or tetrahydronaphile, and the like.
[029] The terms "heteroaryl" and "heteroar-", used alone or as part of a larger portion, for example, "heteroaralkyl", or "heteroaralkoxy", refer to groups that have 5 to 10 ring atoms (or monocyclic or bicyclic), in some modalities 5, 6, 9, or 10 ring atoms. In some modalities, these rings have 6, 10 or 14 π electrons shared in a cyclic arrangement; and which have, in addition to carbon atoms, from one to five hetero atoms. The term "heteroatom" refers to nitrogen, oxygen or sulfur, and includes any oxidized form of nitrogen or sulfur, and any quaternized form of a basic nitrogen. Heteroaryl groups include, but are not limited to, thienyl, furanyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolil, pyridyl, pyridininyl, pyridinyl, pyrimidinyl, pyrimidinyl, pyrimidinyl, pyrimidinyl, pyrimidinyl, pyridinyl, pyridinyl, pyridinyl, pyridinyl, pyridinyl, pyridinyl, pyridinyl, pyridinyl, pyridinyl, pyridinyl, pyrimidinyl, pyrimidinyl, pyrimidine. In some embodiments, a heteroaryl is a heterobyryl group, for example, bipyridyl and the like. The terms "heteroaryl" and "heteroar-", as used herein, also include groups in which a heteroaromatic ring is fused to one or more aryl, cycloaliphatic or heterocyclyl rings, where the radical or point of adhesion is on the heteroaromatic ring. Non-limiting examples include indolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl, indazolyl, benzimidazolyl, benzothiazolyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalin, 4H-quinolinyl, phenyl, quinoline, phenyl, quinoline, phenyl pyrido [2,3-b] -1,4-oxazin-3 (4H) - one. A heteroaryl group can be mono- or bicyclic. The term "heteroaryl" can be used interchangeably with the terms "heteroaryl ring", "heteroaryl group" or "heteroaromatic", any of the terms including rings that are optionally substituted. The term "heteroaralkyl" refers to an alkyl group substituted by a heteroaryl, in which the alkyl and heteroaryl moieties independently are optionally substituted.
[030] As used herein, the terms "heterocycle", "heterocyclyl", "heterocyclic radical" and "heterocyclic ring" are used interchangeably and refer to a stable 5- to 7-membered heterocyclic, monocyclic or bicyclic portion of 7 -10 members which is saturated or partially unsaturated, and which has, in addition to carbon atoms, one or more, preferably one to four, hetero atoms, as defined above. When used in reference to a ring atom on a heterocycle, the term "nitrogen" includes substituted nitrogen. As an example, in a saturated or partially unsaturated ring that has 0-3 heteroatoms selected from oxygen, sulfur or nitrogen, nitrogen can be N (as in 3,4-dihydro-2H-pyrrolyl), NH (as in pyrrolidinyl) or + NR (as in N-substituted pyrrolidinyl).
[031] A heterocyclic ring can be attached to its pendant group on any heteroatom or carbon atom that results in a stable structure and any of the ring atoms can be optionally substituted. Examples of such saturated or partially unsaturated heterocyclic radicals include, without limitation, tetrahydrofuranyl, tetrahydrothiophenyl pyrrolidinyl, piperidinyl, pyrrolinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahidroquinolinil, oxazolidinyl, piperazinil, trilinyl, trilinyl, diazyl, trilinyl, diazyl, trilinyl, diazyl, trilinyl, diazyl, trilinyl, trilinyl, trilinyl, trilinyl, trilinyl, trilinyl, trilinyl, trilinyl, trilinyl, trilinyl, trilinyl, trilinyl. The terms "heterocycle", "heterocyclyl", "heterocyclic ring", "heterocyclic group", "heterocyclic moiety" and "heterocyclic radical", are used interchangeably here, and also include groups in which a heterocyclyl ring is fused to one or more aryl, heteroaryl or cycloaliphatic rings, for example, indolinyl, 3H-indolyl, chromanyl, phenanthridinyl or tetrahydroquinolinyl. A heterocyclyl group can be mono- or bicyclic. The term "heterocyclylalkyl" refers to an alkyl group substituted by a heterocyclyl, wherein the alkyl and heterocyclyl moieties are optionally substituted.
[032] As used herein, the term "partially unsaturated" refers to a portion of the ring that includes at least one double or triple bond. The term "partially unsaturated" is intended to encompass rings that have multiple sites of unsaturation, but is not intended to include aryl or heteroaryl portions, as defined herein.
[033] The term "heteroatom" means one or more of oxygen, sulfur, nitrogen, phosphorus or silicon (including any oxidized form of nitrogen, sulfur, phosphorus or silicon; the quaternized form of any basic nitrogen or; a replaceable nitrogen from a heterocyclic ring, for example, N (as in 3,4-dihydro-2 H - pyrrolyl), NH (as in pyrrolidinyl) or NR + (as in N-substituted pyrrolidinyl)).
[034] The term "unsaturated", as used herein, means that a portion has one or more units of unsaturation.
[035] The term “halogen” means F, Cl, Br or I.
[036] As described herein, the compounds of the invention may contain "optionally substituted" portions. In general, the term "substituted", whether preceded by the term "optionally" or not, means that one or more hydrogens in the designated portion are replaced with a suitable substituent. Unless otherwise indicated, an “optionally substituted” group may have a suitable substituent in each replaceable position in the group and, when more than one position in a certain structure may be replaced with more than one substituent selected from a specified group, the substituent can be the same or different in each position. Combinations of substituents provided for by this invention are preferably those that result in the formation of stable or chemically feasible compounds. The term "stable", as used herein, refers to compounds that are not substantially altered when subjected to conditions that allow their production, detection and, in certain modalities, their recovery, purification and use for one or more of the purposes disclosed herein.
[037] Suitable monovalent substituents on a replaceable carbon atom of an "optionally substituted" group are independently halogen; - (CH2) 0-4Ro; - (CH2) 0-4OR °; -O (CH2) 0-4R °, -O- (CH2) 0-4C (O) OR °; - (CH2) 0- 4CH (OR °) 2; - (CH2) 0-4Ph, which can be replaced with R °; - (CH2) 0-4O (CH2) 0-1Ph which can be replaced with R °; - CH = CHPh, which can be replaced with Ro; - (CH2) 0-4O (CH2) 0-1- pyridyl, which can be replaced with R °; -NO2; - CN; -N3; - (CH2) 0-4N (Ro) 2; - (CH2) 0-4N (RO) C (O) R °; -N (R °) C (S) R °; - (CH2) 0- 4N (R °) C (O) NR ° 2; -N (R °) C (S) NR ° 2; - (CH2) 0-4N (Ro) C (O) OR °; - N (R °) N (R °) C (O) R °; - N (R °) N (R °) C (O) NR ° 2; -N (R °) N (R °) C (O) OR °; - (CH2) C C (O) Ro; -C (S) R °; - (CH2) 0-4C (O) OR °; - (CH2) 0-4C (O) SRo; - (CH2) 0-4C (O) OSiRo3; - (CH2) 0-4OC (O) R °; -OC (O) (CH2) 0-4SR-SC (S) SR °; - (CH2) 0-4SC (O) Ro; - (CH2) 0-4C (O) NR ° 2; -C (S) NR ° 2; - C (S) SR °; -SC (S) SR °, - (CH2) 0-4OC (O) NR ° 2; -C (O) N (OR °) R °; - C (O) C (O) R °; -C (O) CH2C (O) R °; - C (NOR °) R °; - (CH2) 0-4SSR °; - (CH2) 0-4S (O) 2Ro; - (CH2) 0-4S (O) 2OR °; - (CH2) 0-4OS (O) 2R °; - S (O) 2NR ° 2; - (CH2) 0-4S (O) R °; -N (R °) S (O) 2NR ° 2; -N (R °) S (O) 2R °; - N (OR °) R °; - C (NH) NR ° 2; -P (O) 2R °; -P (O) R ° 2; -OP (O) R ° 2; - OP (O) (OR °) 2; -SiR ° 3; -OSiR ° 3; - (C 1-4 straight or branched alkylene) O-N (R °) 2; or - (C1-4 linear or branched alkylene) C (O) ON (R °) 2, where each R ° can be substituted as defined below and is independently hydrogen, aliphatic C1-6, -CH2Ph, -O (CH2 ) 0-1Ph, -CH2- (5-6 membered heteroaryl ring), or a saturated, partially unsaturated or 5-6 membered aryl ring that has 0-4 heteroatoms selected regardless of nitrogen, oxygen or sulfur or, despite the definition above, two independent occurrences of R °, taken together with their intervening atoms, form a saturated, partially unsaturated, mono- or bicyclic 3-12 membered ring that has 0-4 heteroatoms selected independently of nitrogen, oxygen or sulfur , which can be replaced as defined below.
[038] Suitable monovalent substituents on R ° (or on the ring formed by taking two independent occurrences of R ° together with their intervening atoms), are independently halogen, - (CH2) 0-2R *, - (haloR *), - (CH2) 0-2OH, - (CH2) o-2OR *, - (CH2) O-2CH (OR *) 2; - O (haloR *), -CN, -N3, - (CH2) o-2C (O) R *, - (CH2) O-2C (0) OH, - (CH2) O-2C (0) OR * , - (CH2) O-2SR *, - (CH2) O-2SH, - (CH2) 0-2NH2, - (CH2) 0-2NHR *, - (CH2) 0-2NR * 2, -NO2, - SiR * 3, -OSÍR * 3, -C (O) SR *, - (C1-4 straight or branched alkylene) C (O) OR * or -SSR *, where each R * is unsubstituted or, when preceded by “Halo”, is replaced only with one or more halogens, and is independently selected from aliphatic C1-4, -CH2Ph, -O (CH2) o-1Ph, or a 5-6 membered, partially unsaturated or saturated ring that has 0-4 heteroatoms selected independently of nitrogen, oxygen or sulfur. Suitable divalent substituents on a saturated carbon atom of R ° include = O and = S.
[039] Suitable divalent substituents on a saturated carbon atom of an “optionally substituted” group include the following: = O, = S, = NR * 2, = NNHC (O) R *, = NHC (O) OR *, = NNHS (O) 2R *, = NR *, = NOR *, -O (C (R * 2)) 2-3O- or -S (C (R * 2)) 2-3S-, where each occurrence independent of R is selected from hydrogen, C1-6 aliphatic which can be substituted as defined below, or a saturated, partially unsaturated or unsubstituted 5-6 membered ring having 0-4 heteroatoms selected independently of nitrogen, oxygen or sulfur . Suitable divalent substituents that are attached to substitutable carbons neighboring an “optionally substituted” group include: - O (CR * 2) 2-3O-, where each independent occurrence of R is selected from hydrogen, aliphatic C1-6 that can be substituted as defined below, or a saturated, partially unsaturated or unsubstituted 5-6 membered ring having 0-4 heteroatoms selected independently of nitrogen, oxygen or sulfur.
[040] Suitable substituents on the aliphatic group of R * include halogen, -R *, - (haloR *), -OH, -OR *, -O (haloR *), - CN, -C (O) OH, -C (O) OR *, -NH2, -NHR *, -NR% or -NO2, where each R * is unsubstituted or, when preceded by "halo", is replaced only with one or more halogens, and is independently C1 -4 aliphatic, -CH2Ph, -O (CH2) 0-1Ph, or a saturated, partially unsaturated or 5-6 membered aryl ring that has 0-4 heteroatoms selected independently of nitrogen, oxygen or sulfur.
[041] Suitable substituents on a substitutable nitrogen from an “optionally substituted” group include -Rt, -NRt2, -C (O) Rt, -C (O) ORf, -C (O) C (O) Rf, - C (O) CH2C (O) R - S (O) 2R -S (O) 2NRt2, -C (S) NRt2, -C (NH) NRf2 or -N (Rt) S (O) 2Rt; where each Rf is independently hydrogen, C1-6 aliphatic that can be substituted as defined below, unsubstituted -OPh, or a saturated, partially unsaturated or unsubstituted 5-6 membered ring having 0-4 heteroatoms selected regardless of nitrogen, oxygen or sulfur or, despite the definition above, two independent occurrences of Rf, taken together with their intervening atoms, form a saturated, partially unsaturated or unsubstituted 3-12 membered mono- or bicyclic ring that has 0-4 heteroatoms selected independently of nitrogen, oxygen or sulfur.
[042] Suitable substituents on the aliphatic group of Rf are independently halogen, -R *, - (haloR *), -OH, -OR *, -O (haloR *), -CN, -C (O) OH, -C (O) OR *, -NH2, -NHR *, -NR * 2 or - NO2, where each R * is unsubstituted or, when preceded by "halo", is replaced only with one or more halogens, and is independently C1-4 aliphatic, -CH2Ph, -O (CH2) 0-1Ph, or a saturated, partially unsaturated or 5-6 membered aryl ring that has 0-4 heteroatoms selected independently of nitrogen, oxygen or sulfur.
[043] As used herein, the term “stereogenic metal atom” receives its common meaning, and refers to a metal atom coordinated by at least two ligands (for example, at least four ligands), in which the ligands are arranged around the metal atom in such a way that the overall structure (for example, metal complex) is devoid of a plane of symmetry with respect to the metal atom. In some cases, the stereogenic metal atom can be coordinated by at least three ligands, at least four ligands, at least five ligands, at least six ligands, or more. In certain embodiments, the stereogenic metal atom can be coordinated by four ligands. Metal complexes comprising a stereogenic metal center can provide sufficient space specificity at a reaction site of the metal complex, such that a molecular substrate that has a plane of symmetry can be reacted at the reaction site to form a product that it is free of a plane of symmetry. That is, the stereogenic metal center of the metal complex can transmit specificity of sufficient shape to effectively induce stereogenicity, producing a chiral product. These metal complexes can exhibit increased catalytic activity and stereoselectivity over previous systems, and can reduce unwanted side reactions (for example, dimerization or oligomerization of the metal complex).
[044] The term “chiral” receives its common meaning in the art and refers to a molecule that is not superimposable with its specular image, in which the resulting non-superimposable specular images are known as “enantiomers” and are marked as an enantiomer ( R) or as an enantiomer (S). Typically, chiral molecules do not have a plane of symmetry.
[045] The term "achiral" receives its common meaning in the technique and refers to a molecule that is superimposed with its mirror image. Typically, achiral molecules have a plane of symmetry.
[046] As used here, a binder can be monodentate or polyidentate. A linker can have hapticity of more than 1. In some cases, the linker has a hapticity of 1 to 10. For a linker with hapticity greater than 1, as sometimes done in the art, a simple link can be drawn between the linker and the metal. In some cases, a binder is alkylidene. In some cases, a binder is a binder that contains nitrogen. In some cases, a binder is a binder that contains oxygen. In some cases, a binder is a binder that contains phosphorus.
[047] As used here, a "nitrogen-containing binder" can be any species that comprises a nitrogen atom. In some cases, the nitrogen atom can bond to the metal atom. In some cases, the nitrogen-containing binder can attach to the metal center via a different atom. In some cases, the nitrogen atom may be a ring atom of a heteroaryl or heteroalkyl group. In some cases, the nitrogen atom may be an amino-substituted group. It should be understood that, in catalyst precursors described herein, the nitrogen-containing binder may be sufficiently ionic in character to coordinate a metal center, for example, a Mo or W metal center. Examples of nitrogen-containing binders include, without limitation, pyrrolyl, pyrazolyl, pyridinyl, pyrazinyl, pyrimidinyl, imidazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, indolyl, indazolyl, carbazolyl, morpholinyl, piperidinyl, substituted, and derivatives, piperidinyl, substituted and derivatives. For example, the nitrogen-containing binder can be pyrrolid or 2,5-dimethylpyrrolid. The nitrogen-containing binder can be selected to interact with an oxygen-containing binder, such that the oxygen-containing binder can easily replace the nitrogen-containing binder in a pre-catalyst to generate a catalyst. In cases where the catalyst composition can be generated in situ in order to carry out a chemical reaction, the first binder, which contains nitrogen, can be selected in such a way that, by substituting with a binder that contains oxygen, the binders that contain nitrogen or its protonated versions do not interfere with the reaction chemistry. In some embodiments, the nitrogen-containing binder can be chiral and the pre-catalyst can be supplied as a racemic mixture or a purified stereoisomer.
[048] As used herein, the term "oxygen-containing ligand" can be used to refer to ligands that comprise at least one oxygen atom. In some cases, the oxygen atom attaches to the metal atom, thereby forming an ether bond. In other cases, the oxygen-containing binder can attach to the metal center via a different atom. The term "oxygen-containing ligand" can also describe ligand precursors that comprise at least one hydroxyl group (for example, a hydroxyl-containing ligand), in which the deprotonation of the hydroxyl group results in a negatively charged oxygen atom, which can coordinate with a metal atom. The oxygen-containing linker can be a heteroaryl or heteroalkyl group that comprises at least one oxygen atom in the ring. In some cases, the oxygen atom may be positioned on a substituent on an alkyl, heteroalkyl, aryl or heteroaryl group. For example, the oxygen-containing binder may be a hydroxy-substituted aryl group, in which the hydroxyl group is deprotonated after coordination with the metal center.
[049] As used herein, the term "phosphorus-containing ligand" can be used to refer to ligands that comprise at least one phosphorus atom. In some cases, the phosphorus atom binds to the metal. In other cases, the phosphorus-containing binder can attach to the metal center via a different atom (that is, a different phosphorus atom). The phosphorus-containing binder may have a phosphorus atom of various oxidation states. In some cases, the binder that contains phosphorus is phosphine. In some cases, the phosphorus-containing binder is phosphite. In some cases, the phosphorus-containing binder is phosphate. The phosphorus-containing binder can be monodentate or polyidentate. In some cases, two or more phosphorus atoms bind to the metal. In some cases, one or more phosphorus atoms together with one or more different phosphorus atoms bond to the metal.
[050] In many cases, ligand precursors are described that comprise at least one hydroxyl group (for example, a hydroxyl-containing ligand), in which deprotonation of the hydroxyl group results in a negatively charged oxygen atom, which can coordinate with a metal atom. The oxygen-containing linker can be a heteroaryl or heteroalkyl group that comprises at least one oxygen atom in the ring. In some cases, the oxygen atom may be positioned on a substituent on an alkyl, heteroalkyl, aryl or heteroaryl group. For example, the oxygen-containing binder may be a hydroxy-substituted aryl group, in which the hydroxyl group is deprotonated after coordination with the metal center.
[051] As defined herein, a "metal complex" is any complex used to form a supplied precursor complex or any complex generated from a provided precursor complex (for example, for use as a catalyst in a reaction such as, for example, metathesis reaction).
[052] The phrase “protecting group”, as used here, refers to temporary substituents that protect a potentially reactive functional group from unwanted chemical transformations. Examples of such protecting groups include esters of carboxylic acids, silyl ethers of alcohols, and acetals and ketals of aldehydes and ketones, respectively. A "Si protecting group" is a protecting group comprising an Si atom, for example, Si-trialkyl (for example, trimethylsilyl, tributylsilyl, t-butyldimethylsilyl), Si-triaryl, Si-alkyl-diphenyl (eg example, t-butyldiphenylsilyl) or Si-aryl-dialkyl (for example, Si-phenyldialkyl). Usually, a Si protecting group is attached to an oxygen atom. The field of protection group chemistry has been revised (Greene, T.W .; Wuts, P.G.M. “Protective Groups in Organic protection groups (and associated protected portions) are described in detail below.
[053] Protected hydroxyl groups are well known in the art and include those described in detail in "Protecting Groups in Organic Synthesis", T.W. Greene and P.G.M. Wuts, 3rd Edition, John Wiley & Sons, 1999, the entirety of which is incorporated herein by reference. Examples of suitably protected hydroxyl groups further include, without limitation, esters, carbonates, sulfonates, allyl ethers, ethers, silyl ethers, alkyl ethers, arylalkyl ethers and alkoxyalkyl ethers. Examples of suitable esters include formats, acetates, propionates, pentanoates, crotonates and benzoates. Specific examples of suitable esters include formate, benzoyl formate, chloroacetate, trifluoracetate, methoxyacetate, triphenylmethoxyacetate, p-chlorophenoxyacetate, 3-phenylpropionate, 4-oxopentanoate, 4,4- (ethylenedithio) pentanoate, pivaloate, 4-methoxyate -crotonate, benzoate, p-benzylbenzoate, 2,4,6-trimethylbenzoate. Examples of suitable carbonates include 9-fluorenylmethyl, ethyl, 2,2,2-trichloroethyl, 2- (trimethylsilyl) ethyl, 2- (phenylsulfonyl) ethyl, vinyl, ally, and p-nitrobenzyl carbonate. Examples of suitable silyl ethers include trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, t-butyldiphenylsilyl, triisopropylsilyl ether, and other trialkylsilyl ethers. Examples of suitable alkyl ethers include methyl, benzyl, p-methoxybenzyl, 3,4-dimethoxybenzyl, trityl, t-butyl and allyl ether, or derivatives thereof. Alkoxyalkyl ethers include acetals such as, for example, methoxymethyl, methylthiomethyl, (2- (trimethylsilyl) ethoxymethyl and tetrahydropyran-2-yl ether. Examples of suitable arylalkyl ethers include benzyl, p-methoxybenzyl (MPM), 3,4-dimethoxybenzyl, O -nitrobenzyl, p-nitrobenzyl, p-halobenzyl, 2,6-dichlorobenzyl, p-cyanobenzyl, 2- and 4-picolyl ethers.
[054] Protected amines are well known in the art and include those described in detail in Greene (1999). Suitable monoprotected amines further include, without limitation, aralkylamines, carbamates, allyl amines, amides, and the like. Examples of suitable monoprotected amino moieties include t-butyloxycarbonylamino (-NHBOC), ethyloxycarbonylamino, methyloxycarbonylamino, trichloroethyloxycarbonylamino, allyloxycarbonylamino (- NHAloc), benzyloxycarbonylamino (-NHCBZ), acetyl-aminamino, , chloroacetamido, dichloroacetamido, trichloroacetamido, phenylacetamido, trifluoracetamido, benzamido, t-butyldiphenylsilyl, and the like. Suitable diprotected amines include amines that are substituted with two substituents selected independently from those described above as monoprotected amines, and further include cyclic imides, for example, phthalimide, maleimide, succinimide, and the like. Suitable diprotected amines also include pyrroles and the like, 2,2,5,5-tetramethyl- [1,2,5] azadisilolidine and the like, and azide.
[055] Protected aldehydes are well known in the art and include those described in detail in Greene (1999). Suitable protected aldehydes further include, without limitation, acyclic acetals, cyclic acetals, hydrazones, imines, and the like. Examples of such groups include dimethyl acetal, diethyl acetal, diisopropyl acetal, dibenzyl acetal, bis (2-nitrobenzyl) acetal, 1,3-dioxanes, 1,3-dioxolanes, semicarbazones, and derivatives thereof.
[056] Protected carboxylic acids are well known in the art and include those described in detail in Greene (1999). Protected carboxylic acids further include, without limitation, optionally substituted aliphatic C1-6 esters, optionally substituted aryl esters, silyl esters, activated esters, amides, hydrazides, and the like. Examples of such ester groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, benzyl and phenyl ester, where each group is optionally substituted. Additional suitable protected carboxylic acids include oxazolines and orthoesters.
[057] Protected thiols are well known in the art and include those described in detail in Greene (1999). Suitable protected thiols further include, without limitation, disulfides, thioethers, silyl thioethers, thioesters, thiocarbonates and thiocarbamates, and the like. Examples of such groups include, without limitation, alkyl thioethers, benzyl and substituted benzyl thioethers, triphenylmethyl thioethers and trichloroethoxycarbonyl thioester, just to name a few. 3. Description of certain embodiments of the invention
[058] In some embodiments, the present invention provides complexes that serve as precursors for metathesis catalysts, including stereogenic metal catalysts. In certain embodiments, the precursor complexes provided are used in metathesis reactions, for example, olefin metathesis reactions.
[059] As used herein, the term "metathesis reaction" receives its common significance in the art and refers to a reaction chemistry in which its reactive species exchange partners in the presence of a transition metal catalyst. In some cases, a by-product of a metathesis reaction may be ethylene. A metathesis reaction may involve the reaction between species that comprise, for example, olefins and / or alkynes. Examples of different types of metathesis reactions include cross metathesis, ring closing metathesis, ring opening metathesis, acyclic diene metathesis, alkaline metathesis, enino metathesis, and the like. The metathesis reaction can occur between two substrates that are not joined by a bond (for example, intermolecular metathesis reaction) or between two portions of a single substrate (for example, intramolecular metathesis reaction). In some embodiments, the complexes of the present invention are useful in forming a metathesis product with high enantioselectivity and / or a high proportion of Z: E isomers, and / or a high proportion of E: Z isomers.
[060] In some embodiments, a compound is isolated as a Lewis base adduct. The terms "Lewis base" and "Lewis base adduct" are known in the art and refer to a chemical moiety capable of donating an electron pair to another chemical moiety. In some embodiments, the coordination of Lewis base molecules with a compound can result in a complex that has a plane of symmetry with respect to the metal center. However, a stereogenic metal center can be formed by easily removing the Lewis base molecules and / or replacing one or more Lewis base molecules with one or more molecules that cause the complex to lose its plane of symmetry with relation to the metal center. For example, the revealed compound can be formed and stored as a Lewis base adduct, and can be "activated" in a subsequent reaction step to generate a catalyst with a stereogenic metal center.
[061] Some embodiments of the invention provide a composition comprising a precursor complex provided which, upon treatment to generate a metal complex, generates a catalyst suitable for use in the reactions described herein. In some embodiments, the treatment of the precursor complex provided generates a metal complex that comprises a stereogenic metal atom and two or more ligands that bind to the metal atom. In some embodiments, each binder associated with the metal complex comprises an organic group. The binders can be monodentate binders, that is, the binders bind to the stereogenic metal atom via a linker site (for example, a carbon atom or a heteroatom of the linker). In some embodiments, a monodentate binder can be attached to the metal center through a single bond or a multiple bond. In some embodiments, the metal complex comprises at least one binder devoid of a plane of symmetry. That is, at least one linker attached to the stereogenic metal atom is a chiral linker. In some embodiments, the metal complex comprises a nitrogen-containing binder, including chiral and / or aquiral nitrogen-containing binders. For example, the linker can be a chiral or achiral nitrogen heterocycle, for example, a pyrrolidide. In some embodiments, the metal complex comprises a binder that contains oxygen, including chiral and / or achiral binders that contain oxygen. For example, the linker can be a chiral or achiral biphenyl group substituted with at least an oxygen-containing moiety, for example, a phenol. In some cases, the metal atom may be attached to at least one carbon atom. In some embodiments, the metal complex comprises a binder that contains phosphorus, including chiral and / or achiral binders that contain oxygen.
[062] Some aspects of the invention can be realized with complex precursors provided that comprise two or more ligands, in which each ligand is a monodentate ligand, that is, each ligand binds or coordinates with the metal center through a site coordination of the metal only, or through a binder site only. In some embodiments, a precursor complex provided comprises primarily monodentate ligands. In some embodiments, a precursor complex provided comprises at least one bidentate ligand, that is, the ligand binds or coordinates with the metal center through two coordination sites. In some embodiments, a precursor complex provided comprises a monodentate ligand and a bidentate ligand.
[063] In some embodiments, the methods of the present invention include the use of a compound disclosed herein, by generating a metal complex in situ, the metal complex is present in a diastereomeric ratio greater than 1: 1. In some embodiments, the metal complex is present in a diastereomeric ratio greater than about 5: 1, greater than about 7: 1, greater than about 10: 1, greater than about 20: 1 or, in some cases, greater. In certain embodiments, the metal complex generated in situ is an active catalyst metal complex. Exemplary active catalyst metal complexes include metal complexes described herein for use, inter alia, in olefin metathesis reactions.
[064] In some embodiments, the present invention provides a compound of formula I:
where: each of R1 and R2 is independently R, -OR, -SR, - N (R) 2, -OC (O) R, -SOR, -SO2R, - SO2N (R) 2, -C (O ) N (R) 2, - NRC (O) R or -NRSO2R; each of R3 and R4 is independently halogen, R, - N (R) 2, -NRC (O) R, -NRC (O) OR, - NRC (O) N (R) 2, -NRSO2R, - NRSO2N ( R) 2, -NROR, NR3, -OR, O (R) 2, a linker that contains phosphorus, or an optionally substituted group selected from a 5-6 membered heteroaryl monocyclic ring that has at least one nitrogen and 0-3 additional heteroatoms selected independently of nitrogen, oxygen or sulfur, a 4-7 membered saturated or partially unsaturated heterocyclic ring that has at least one nitrogen and 0-2 additional heteroatoms selected independently of nitrogen, oxygen or sulfur, a saturated bicyclic heterocyclic ring or partially unsaturated 7-10 member that has at least one nitrogen and 0-4 additional heteroatoms selected independently of nitrogen, oxygen or sulfur or an 8-10 membered bicyclic heteroaryl ring that has at least one nitrogen and 0-4 additional selected heteroatoms regardless of nitrogen, oxygen the u sulfur; each R is independently hydrogen or an optionally substituted group selected from C1-20 aliphatic, C120 heteroaliphatic having 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, phenyl, ferrocene, a 3-7 membered saturated or partially unsaturated carbocyclic ring , an 8-10 membered saturated, partially unsaturated or aryl bicyclic ring, a 5-6 membered heteroaryl monocyclic ring that has 14 heteroatoms independently selected from nitrogen, oxygen or sulfur, a 4-7 membered saturated or partially unsaturated heterocyclic ring which has 1-3 heteroatoms selected independently of nitrogen, oxygen or sulfur, a 7-10 membered saturated or partially unsaturated bicyclic heterocyclic ring which has 1-5 heteroatoms selected independently of nitrogen, oxygen or sulfur or an 8- bicyclic heteroaryl ring 10 members that have 1-5 heteroatoms selected independently of nitrogen, oxygen or sulfur, or: two or three R groups on the same nitrogen atom are taken together with nitrogen to form an optionally substituted 3-12 membered saturated, partially unsaturated or aryl ring that has 0-5 additional hetero atoms, not including the same nitrogen atom, selected independently of nitrogen, oxygen or sulfur; or: two R groups on the same oxygen atom are taken together with oxygen to form an optionally substituted saturated, partially unsaturated or 3-12 membered aryl ring that has 0-5 additional heteroatoms, not including the same oxygen atom, independently selected from nitrogen, oxygen or sulfur; n is 0, 1 or 2; each R5 is independently a monodentate ligand, or two R5 are taken together with their intervening atoms to form an optionally substituted bidentate group; and two or more of R1, R2, R3, R4 and R5 can be taken together with their intervening atoms to form an optionally substituted polyidentated ligand.
[065] As generally defined above, each of R1 and R2 is independently R, -OR, -SR, - N (R) 2, -OC (O) R, -SOR, - SO2R, -SO2N (R) 2 , -C (O) N (R) 2, -NRC (O) R or -NRSO2R, where R is hydrogen, or an optionally substituted group selected from C1-20 aliphatic, C1-20 heteroaliphatic that has 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, an 8-10 membered saturated, partially unsaturated or aryl bicyclic ring, a 5-6 membered heteroaryl monocyclic ring that has 1-4 heteroatoms selected independently of nitrogen, oxygen or sulfur, a 4-7 membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms selected independently of nitrogen, oxygen or sulfur, a saturated or partially unsaturated 7-membered heterocyclic ring -10 members that have 1-5 heteroatoms selected independently of nitrogen, oxygen or sulfur or an 8-10 membered bicyclic heteroaryl ring that has 1-5 heteroatoms selected independently of nitrogen, oxygen or sulfur.
[066] In some modalities, both R1 and R2 are hydrogen. In some embodiments, one of R1 and R2 is hydrogen and the other is an optionally substituted group selected from C1-20 aliphatic, C1-20 heteroaliphatic which has 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, phenyl, a carbocyclic ring saturated or partially unsaturated 3-7 membered, a saturated, partially unsaturated or aryl 8-10 membered bicyclic ring, a 5-6 membered heteroaryl monocyclic ring that has 1-4 heteroatoms selected independently of nitrogen, oxygen or sulfur, a 4-7 membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, a 7-10 membered saturated or partially unsaturated heterocyclic ring having 1-5 heteroatoms selected independently of nitrogen, oxygen or sulfur or an 8-10 membered bicyclic heteroaryl ring that has 1-5 heteroatoms selected regardless of nitrogen, oxygen or sulfur.
[067] In certain embodiments, the R1 group or the R2 group of formula I is optionally substituted C1-20 aliphatic. In some embodiments, R1 or R2 is optionally substituted C1-20 alkyl. In certain embodiments, R1 or R2 is C1-6 alkyl substituted with phenyl and one or two additional substituents. In certain embodiments, R1 or R2 is a lower alkyl group optionally substituted with one or two methyl and phenyl groups. In certain embodiments, R1 or R2 is - C (Me) 2Ph. In certain embodiments, R1 or R2 is -C (Me) 3. In some embodiments, R1 or R2 is selected from any of those groups R1 or R2 disclosed or described herein.
[068] In certain embodiments, R2 is hydrogen and R1 is R, -OR, -SR, -N (R) 2, - OC (O) R, -SOR, -SO2R, -SO2N (R) 2, - C (O) N (R) 2, -NRC (O) R or -NRSO2R, where each R is independently as defined above and described herein. In certain embodiments, R2 is hydrogen and R1 is R, where R is as defined above and described herein. In certain embodiments, R2 is hydrogen and R1 is optionally substituted aliphatic C1-20. In some embodiments, R2 is hydrogen and R1 is optionally substituted C1-20 alkyl. In certain embodiments, R2 is hydrogen and R1 is C1-6 alkyl substituted with phenyl and one or two additional substituents. In certain embodiments, R2 is hydrogen and R1 is a lower alkyl group optionally substituted with one or two methyl and phenyl groups. In certain embodiments, R2 is hydrogen and R1 is - C (Me) 2Ph. In certain embodiments, R2 is hydrogen and R1 is - C (Me) 3. In some embodiments, R2 is hydrogen and R1 is selected from any of those groups R1 or R2 disclosed or described herein.
[069] In some modalities,
wherein each of n, R1, R3, R4 and R5 is as defined above and described in embodiments herein, either alone or in combination. In some embodiments, both R1 and R2 are hydrogen.
[070] As generally defined above, each R3 and R4 is halogen, R, -N (R) 2, -NRC (O) R, - NRC (O) OR, -NRC (O) N (R) 2, - NRSO2R, -NRSO2N (R) 2, -NROR, NR3, -OR, O (R) 2, a linker that contains phosphorus, or an optionally substituted group selected from a 5-6 membered heteroaryl monocyclic ring that has at least one nitrogen and 0-3 additional heteroatoms selected independently of nitrogen, oxygen or sulfur, a 4-7 membered saturated or partially unsaturated heterocyclic ring that has at least one nitrogen and 0-2 additional heteroatoms selected independently of nitrogen, oxygen or sulfur, one 7-10 membered saturated or partially unsaturated bicyclic heterocyclic ring that has at least one nitrogen and 0-4 additional heteroatoms independently selected from nitrogen, oxygen or sulfur or an 8-10 membered bicyclic heteroaryl ring that has at least one nitrogen and 0 -4 additional heteroatoms selected independently of nitrogen o, oxygen or sulfur, where each R is independently as defined above or described herein.
[071] In some modalities, at least one of R3 and R4 is halogen. In other embodiments, each R3 and R4 is independently R, -N (R) 2, -NRC (O) R, -NRC (O) OR, - NRC (O) N (R) 2, -NRSO2R, -NRSO2N ( R) 2, -NROR, NR3, -OR, O (R) 2, a linker that contains phosphorus, or an optionally substituted group selected from a 5-6 membered heteroaryl monocyclic ring that has at least one nitrogen and 0-3 additional heteroatoms selected independently of nitrogen, oxygen or sulfur, a 4-7 membered saturated or partially unsaturated heterocyclic ring that has at least one nitrogen and 0-2 additional heteroatoms selected independently of nitrogen, oxygen or sulfur, a saturated bicyclic heterocyclic ring or partially unsaturated 7-10 member that has at least one nitrogen and 0-4 additional heteroatoms selected independently of nitrogen, oxygen or sulfur or an 8-10 membered bicyclic heteroaryl ring that has at least one nitrogen and 0-4 additional selected heteroatoms regardless of nitrogen, oxygen io or sulfur, where each R is independently as defined above or described herein.
[072] In certain modalities, at least one of R3 and R4 is -N (R) 2. In some embodiments, both R3 and R4 are - N (R) 2, where one R is hydrogen and the other is optionally substituted aliphatic C1-20.
[073] In other embodiments, R3 and R4 are -N (R) 2, where the two R groups are taken together with nitrogen to form an optionally substituted 3-8 membered saturated, partially unsaturated or aryl ring that has 03 additional heteroatoms, not including the N atom of N (R) 2, independently selected from nitrogen, oxygen or sulfur, where R3 and R4 are coordinated with W by means of a nitrogen. In some embodiments, the two R groups are taken together with nitrogen to form an optionally substituted 5-membered heteroaryl ring that has 0-3 additional nitrogen atoms, not including the N atom of N (R) 2. Such rings include optionally substituted pyrrol-1-yl, pyrazol-1-yl, imidazol-1-yl and triazol-1-yl. In some embodiments, these rings are unsubstituted pyrrol-1-yl, pyrazol-1-yl, imidazol-1-yl and triazol-1-yl.
[074] In some embodiments, at least one of R3 and R4 is an optionally substituted 5-6 membered heteroaryl monocyclic ring that has at least one nitrogen and 0-3 additional heteroatoms selected independently of nitrogen, oxygen or sulfur. In some embodiments, at least one of R3 and R4 is an optionally substituted group selected from pyrrolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, isoxazoil, oxadiazoyl, thiazolyl and thiazolyl. In some embodiments, at least one of R3 and R4 is an unsubstituted group selected from pyrrolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, isoxazolyl, oxadiazoyl, thiazolyl and thiazolyl. In some embodiments, at least one of R3 and R4 is a substituted group selected from pyrrolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl and thiazolyl. In some embodiments, at least one of R3 and R4 is an unsubstituted pyrrolyl. In some embodiments, each of R3 and R4 is an unsubstituted pyrrolyl. In some embodiments, at least one of R3 and R4 is a substituted pyrrolyl. In some embodiments, each of R3 and R4 is a substituted pyrrolyl.
[075] In other embodiments, at least one of R3 and R4 is an optionally substituted 8-10 membered bicyclic heteroaryl ring that has at least one nitrogen and 0-4 additional heteroatoms selected independently of nitrogen, oxygen or sulfur. In some embodiments, at least one of R3 and R4 is an optionally substituted group selected from indolyl, benzimidazolyl and indazolyl. In some embodiments, at least one of R3 and R4 is an unsubstituted group selected from indolyl, benzimidazolyl and indazolyl. In some embodiments, at least one of R3 and R4 is a substituted group selected from indolyl, benzimidazolyl and indazolyl.
[076] In certain embodiments, at least one of R3 and R4 is an optionally substituted group selected from:
where, or where each represents the point of adhesion to the metal. In some modalities at least one of R3 and R4 is an unsubstituted group selected from:

[077] In some modalities, at least one of R and R4 is a substituted group selected from:

[078] In some embodiments, at least one of R3 and R4 is -OR, where R is as defined above or described here. In some embodiments, at least one of R3 and R4 is -OR, where R is hydrogen. In some embodiments, at least one of R3 and R4 is -OR, where R is an optionally substituted group selected from C1-20 aliphatic, C1-20 heteroaliphatic having 1-3 heteroatoms selected independently of nitrogen, oxygen or sulfur, phenyl , ferrocene, a 3-7 membered saturated or partially unsaturated carbocyclic ring, an 8-10 membered saturated, partially unsaturated or aryl ring, a 5-6 membered heteroaryl monocyclic ring that has 1-4 heteroatoms selected regardless of nitrogen , oxygen or sulfur, a 4-7 membered saturated or partially unsaturated heterocyclic ring that has 1-3 heteroatoms selected independently of nitrogen, oxygen or sulfur, a 7-10 membered saturated or partially unsaturated heterocyclic ring that has 1-5 heteroatoms selected independently of nitrogen, oxygen or sulfur or an 8-14 membered bicyclic or tricyclic heteroaryl ring having 1-5 sele heteroatoms independently of nitrogen, oxygen or sulfur. In some embodiments, at least one of R3 and R4 is -OR, where R is an optionally substituted aliphatic C1-20. In some embodiments, at least one of R3 and R4 is -OR, where R is an optionally substituted heteroaliphatic C1-20 that has 1-3 heteroatoms selected independently of nitrogen, oxygen or sulfur. In some embodiments, at least one of R3 and R4 is -OR, where R is an optionally substituted phenyl. In some embodiments, at least one of R3 and R4 is -OR, where R is an optionally substituted 37-membered saturated or partially unsaturated carbocyclic ring. In some embodiments, at least one of R3 and R4 is -OR, where R is a saturated, partially unsaturated or optionally substituted 8-10 membered aryl ring. In some embodiments, at least one of R3 and R4 is -OR, where R is an optionally substituted 5-6 membered heteroaryl monocyclic ring that has 1-4 heteroatoms selected independently of nitrogen, oxygen or sulfur. In some embodiments, at least one of R3 and R4 is -OR, where R is an optionally substituted 4-7 membered saturated or partially unsaturated heterocyclic ring that has 1-3 heteroatoms selected independently of nitrogen, oxygen or sulfur. In some embodiments, at least one of R3 and R4 is -OR, where R is an optionally substituted 7-10 membered saturated or partially unsaturated bicyclic heterocyclic ring that has 1-5 heteroatoms selected independently of nitrogen, oxygen or sulfur. In some embodiments, at least one of R3 and R4 is -OR, where R is an optionally substituted 8-14 membered bicyclic or tricyclic heteroaryl ring that has 1-5 heteroatoms selected independently of nitrogen, oxygen or sulfur.
[079] In certain embodiments, at least one of R3 and R4 is -OR, where R is an optionally substituted phenyl. In some embodiments, at least one of R3 and R4 is phenoxide. In certain embodiments, at least one of R3 and R4 is -OR, where R is a substituted phenyl. In certain embodiments, at least one of R3 and R4 is -OR, where R is a phenyl substituted with one or more optionally substituted alkyl groups. In certain embodiments, at least one of R3 and R4 is -OR, where R is 2,6-disubstituted phenyl with two optionally substituted alkyl substituents. In certain embodiments, at least one of R3 and R4 is -OR, where R is phenyl 2,4,6-tri-substituted with three optionally substituted alkyl substituents. In certain embodiments, at least one of R3 and R4 is -OR, where R is a phenyl substituted with one or more optionally substituted aryl groups. In certain embodiments, at least one of R3 and R4 is -OR, where R is 2,6-disubstituted phenyl with two optionally substituted aryl substituents. In certain embodiments, at least one of R3 and R4 is -OR, where R is phenyl 2,4,6-tri-substituted with three optionally substituted aryl substituents. In certain embodiments, at least one of R3 and R4 is -OR, where R is a phenyl substituted with one or more optionally substituted phenyl groups. In certain embodiments, at least one of R3 and R4 is -OR, where R is 2,6-disubstituted phenyl with two optionally substituted phenyl substituents. In certain embodiments, at least one of R3 and R4 is -OR, where R is phenyl 2,4,6-tri-substituted with three optionally substituted phenyl substituents. In certain embodiments, at least one of R3 and R4 is O-2,6-dimesithylphenoxide (OHMT). In certain embodiments, at least one of R3 and R4 is O-2,6- (2,4,6-triisopropylphenyl) 2C6H3 (OHIPT). In certain embodiments, at least one of R3 and R4 is 2,6-pentafluorfenylphenoxide (DFTO or decafluorterphenoxide).
[080] In certain embodiments, at least one of R3 and R4 is O (R) 2 where each R is independently as defined above or described herein.
[081] In certain embodiments, at least one of R3 and R4 is O (R) 2, where each R is independently hydrogen or an optionally substituted group selected from C1-20 aliphatic, C1-20 heteroaliphatic which has 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, phenyl, ferrocene, a 3-7 membered saturated or partially unsaturated carbocyclic ring, an 8-10 membered saturated, partially unsaturated bicyclic ring, a 5-6 membered heteroaryl monocyclic ring which has 14 hetero atoms independently selected from nitrogen, oxygen or sulfur, a 4-7 membered saturated or partially unsaturated heterocyclic ring which has 1-3 hetero atoms independently selected from nitrogen, oxygen or sulfur, a saturated or partially unsaturated bicyclic heterocyclic ring of 7 -10 members having 1-5 heteroatoms selected independently of nitrogen, oxygen or sulfur or an 8-10 membered bicyclic heteroaryl ring that has 1-5 heteroatoms selected independently of nitrogen, oxygen or sulfur.
[082] In certain embodiments, at least one of R3 and R4 is O (R) 2, where two R groups on the same oxygen atom are taken together with oxygen to form a saturated, partially unsaturated or aryl ring of 3 -12 optionally substituted members that have 0-5 additional hetero atoms, not including the same oxygen atom, selected independently of nitrogen, oxygen or sulfur.
[083] In certain embodiments, at least one of R3 and R4 is independently N (R) 3, where each R is independently as defined above or described herein. In certain embodiments, at least one of R3 and R4 is independently N (R) 3, where each R is independently hydrogen or an optionally substituted group selected from C1-20 aliphatic, phenyl, ferrocene, a saturated or partially unsaturated carbocyclic ring of 3-7 members, a saturated, partially unsaturated or aryl 8-10 membered bicyclic ring, a 5-6 membered heteroaryl monocyclic ring having 1-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, a partially or saturated heterocyclic ring 4-7 membered unsaturated that has 1-3 heteroatoms selected independently of nitrogen, oxygen or sulfur, a saturated or partially unsaturated 7-10 membered heterocyclic ring that has 1-5 selected heteroatoms regardless of nitrogen, oxygen or sulfur or one 8-10 membered bicyclic or tricyclic heteroaryl ring having 1-5 heteroatoms selected independently of nitrogen, oxygen or sulfur . In some embodiments, one group R is hydrogen and the other two are independently an optionally substituted group selected from phenyl, naphthyl, cyclohexyl, pyridyl, pyrimidinyl, cyclopentyl, methyl, ethyl, propyl or butyl.
[084] In certain embodiments, at least one of R3 and R4 is independently N (R) 3, in which the two or three R groups are taken together with the nitrogen atom to form a saturated, partially unsaturated or aryl ring. 3-12 optionally substituted members that have 0-5 additional hetero atoms, not including the N atom of N (R) 3, selected independently of nitrogen, oxygen or sulfur. In some embodiments, two or three R groups are taken together with nitrogen to form an optionally substituted 5-membered heteroaryl ring that has 1-3 nitrogen atoms. These rings include optionally substituted pyrrole, pyrazole, imidazole and triazole.
[085] In some embodiments, at least one of R3 and R4 is independently a binder that contains phosphorus. In some embodiments, at least one of R3 and R4 is independently a phosphorus-containing ligand capable of coordinating with W via the phosphorus atom. In some embodiments, at least one of R3 and R4 is independently -P (R ') 2, P (R') 3, - P (O) (R ') 2, P (O) (R') 3, in that: each R 'is independently halogen, -R, -OR, - N (R) 2, or two or three R' are taken together with the phosphorus to form a 3-20 membered ring optionally substituted with 0-10 additional hetero atoms, not including the phosphorus atom of -P (R ') 2, P (R') 3, -P (O) (R ') 2 or P (O) (R') 3, independently selected from nitrogen , oxygen, sulfur or phosphorus; and each R is independently hydrogen or an optionally substituted group selected from C1-20 aliphatic, C1-20 heteroaliphatic having 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, phenyl, ferrocene, a saturated or partially unsaturated carbocyclic ring of 3 -7 members, a saturated, partially unsaturated or aryl 8-10 membered bicyclic ring, a 5-6 membered heteroaryl monocyclic ring having 1-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, a saturated or partially unsaturated heterocyclic ring 4-7 membered having 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, a saturated or partially unsaturated 7-10 membered heterocyclic ring having 1-5 heteroatoms independently selected from nitrogen, oxygen or sulfur or a ring 8-10 membered bicyclic heteroaryl that has 1-5 heteroatoms selected independently of nitrogen io, oxygen or sulfur, or: two or three R groups on the same nitrogen atom are taken together with nitrogen to form an optionally substituted saturated, partially unsaturated or 3-12 membered aryl ring that has 0-5 additional hetero atoms, not including the same nitrogen atom, independently selected from nitrogen, oxygen or sulfur; or: two R groups on the same oxygen atom are taken together with oxygen to form an optionally substituted saturated, partially unsaturated or 3-12 membered aryl ring that has 0-5 additional heteroatoms, not including the same oxygen atom, independently of nitrogen, oxygen or sulfur.
[086] In some embodiments, at least one of R3 and R4 is independently P (R ') 3, where each R' is independently as defined above and described herein. In some embodiments, at least one of R3 and R4 is independently P (R ') 3, where each R' is R and where R is as defined above and described herein. In some embodiments, at least one of R3 and R4 is independently P (R ') 3, where each R' is an optionally substituted group selected from hydrogen, aliphatic C1-20, phenyl or ferrocene.
[087] In some modalities, at least one of R3 or R4 is partially dissociated.
[088] In some embodiments, R3 is halogen or -OR, where R is as defined above and described here. In some embodiments, R3 is halogen. In some embodiments, R3 is - OR, where R is as defined above and described here. In some embodiments, R3 is -OR, where R is hydrogen. In some embodiments, R3 is -OR, where R is an optionally substituted group selected from C1-20 aliphatic, C120 heteroaliphatic having 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, phenyl, ferrocene, a saturated carbocyclic ring or partially unsaturated 3-7 membered, a saturated bicyclic ring, partially unsaturated or 8-10 membered aryl, a 5-6 membered heteroaryl monocyclic ring that has 14 heteroatoms independently selected from nitrogen, oxygen or sulfur, a saturated heterocyclic ring or partially unsaturated 4-7 member that has 1-3 hetero atoms independently selected from nitrogen, oxygen or sulfur, a saturated or partially unsaturated 7-10 membered heterocyclic ring that has 1-5 hetero atoms selected regardless of nitrogen, oxygen or sulfur or an 8-10 membered bicyclic heteroaryl ring that has 1-5 heteroatoms selected independently of nitrogen io, oxygen or sulfur. In some embodiments, R3 is -OR, where R is an optionally substituted aliphatic C1-20. In some embodiments, R3 is -OR, where R is an optionally substituted heteroaliphatic C1-20 that has 1-3 heteroatoms selected independently of nitrogen, oxygen or sulfur. In some embodiments, R3 is -OR, where R is an optionally substituted phenyl. In some embodiments, R3 is -OR, where R is an optionally substituted 3-7 membered saturated or partially unsaturated carbocyclic ring. In some embodiments, R3 is - OR, where R is a saturated, partially unsaturated or optionally substituted 8-10 membered aryl ring. In some embodiments, R3 is -OR, where R is an optionally substituted 5-6 membered heteroaryl monocyclic ring that has 1-4 heteroatoms selected independently of nitrogen, oxygen or sulfur. In some embodiments, R3 is -OR, where R is an optionally substituted 4-7 membered saturated or partially unsaturated heterocyclic ring that has 1-3 heteroatoms selected independently of nitrogen, oxygen or sulfur. In some embodiments, R3 is -OR, where R is an optionally substituted 7-10 membered saturated or partially unsaturated bicyclic heterocyclic ring that has 1-5 heteroatoms selected independently of nitrogen, oxygen or sulfur. In some embodiments, R3 is -OR, where R is an optionally substituted 8-14 membered bicyclic or tricyclic heteroaryl ring that has 1-5 heteroatoms selected independently of nitrogen, oxygen or sulfur.
[089] In some embodiments, R3 is -OR, where R is an optionally substituted phenyl. In some embodiments, R3 is phenoxide. In certain embodiments, R3 is -OR, where R is a substituted phenyl. In certain embodiments, R3 is -OR, where R is a phenyl substituted with one or more optionally substituted alkyl groups. In certain embodiments, R3 is - OR, where R is 2,6-disubstituted phenyl with two optionally substituted alkyl substituents. In certain embodiments, R3 is -OR, where R is phenyl 2,4,6-tri-substituted with three optionally substituted alkyl substituents. In certain embodiments, R3 is -OR, where R is a phenyl substituted with one or more optionally substituted aryl groups. In certain embodiments, R3 is - OR, where R is 2,6-disubstituted phenyl with two optionally substituted aryl substituents. In certain embodiments, R3 is -OR, where R is phenyl 2,4,6-tri-substituted with three optionally substituted aryl substituents. In certain embodiments, R3 is -OR, where R is a phenyl substituted with one or more optionally substituted phenyl groups. In certain embodiments, R3 is - OR, where R is 2,6-disubstituted phenyl with two optionally substituted phenyl substituents. In certain embodiments, R3 is -OR, where R is phenyl 2,4,6-tri-substituted with three optionally substituted phenyl substituents. In certain embodiments R3 is O-2,6-dimesithylphenoxide (OHMT). In certain embodiments R3 is O-2,6- (2,4,6-triisopropylphenyl) 2C6H3 (OHIPT). In some embodiments, R3 is not -O-2,6-Ph2C6H3. In some embodiments, R3 is 2,6-pentafluorfenylphenoxide (DFTO or decafluorterphenoxide).
[090] In some modalities, R3 is an optionally substituted group selected from:
where each represents the point of adhesion to W. In other embodiments, R3 is an optionally substituted portion. In some embodiments, R3 is optionally replaced with one or more electron withdrawal groups. In some embodiments, R3 is optionally substituted with one or more halogens. In some embodiments, R3 is optionally substituted with one or more - F. In some embodiments, R3 is optionally substituted with one or more -Cl. In some embodiments, R3 is optionally replaced with one or more -Br. In some embodiments, R3 is optionally replaced with one or more -I.
[091] Exemplary R3 groups are revealed below, with each representing the point of adhesion to the metal
:
[092] In some embodiments, R4 is halogen, R, - N (R) 2, -NRC (O) R, -NRC (O) OR, - NRC (O) N (R) 2, -NRSO2R, - NRSO2N (R) 2, -NROR, NR3, -OR, O (R) 2, a linker that contains phosphorus, or an optionally substituted group selected from a 5-6 membered heteroaryl monocyclic ring that has at least one nitrogen and 0- 3 additional heteroatoms selected independently of nitrogen, oxygen or sulfur, a 4-7 membered saturated or partially unsaturated heterocyclic ring that has at least one nitrogen and 0-2 additional heteroatoms selected independently of nitrogen, oxygen or sulfur, a saturated bicyclic heterocyclic ring or partially unsaturated 7-10 member that has at least one nitrogen and 0-4 additional heteroatoms independently selected from nitrogen, oxygen or sulfur or an 8-10 membered bicyclic heteroaryl ring that has at least one nitrogen and 0-4 additional hetero atoms independently of nitrogen, oxygen or en sulfur, where each R is independently as defined above and described herein.
[093] In some embodiments, R4 is -N (R) 2, -NRC (O) R, - NRC (O) OR, -NRC (O) N (R) 2, -NRSO2R, -NRSO2N (R) 2 or -NROR, or an optionally substituted group selected from a 5-6 membered heteroaryl monocyclic ring that has at least one nitrogen and 0-3 additional heteroatoms independently selected from nitrogen, oxygen or sulfur, a saturated or partially unsaturated heterocyclic ring of 4 -7 members that have at least one nitrogen and 0-2 additional heteroatoms selected independently of nitrogen, oxygen or sulfur, a 7-10 membered saturated or partially unsaturated bicyclic heterocyclic ring that has at least one nitrogen and 0-4 additional selected heteroatoms regardless of nitrogen, oxygen or sulfur or an 8-10 membered bicyclic heteroaryl ring that has at least one nitrogen and 0-4 additional heteroatoms selected independently of nitrogen, oxygen or sulfur, where each R is independently as defined above and described here.
[094] In certain embodiments, R4 is halogen. In some embodiments, R4 is -N (R) 2. In some embodiments, R4 is an optionally substituted 5-6 membered heteroaryl monocyclic ring that has at least one nitrogen and 0-3 additional heteroatoms selected independently of nitrogen, oxygen or sulfur. In some embodiments, R4 is an optionally substituted 4-7 membered saturated or partially unsaturated heterocyclic ring that has at least one nitrogen and 0-2 additional heteroatoms selected independently of nitrogen, oxygen or sulfur. In some embodiments, R4 is an optionally substituted 7-10 membered saturated or partially unsaturated bicyclic heterocyclic ring that has at least one nitrogen and 0-4 additional heteroatoms selected independently of nitrogen, oxygen or sulfur. In some embodiments, R4 is an optionally substituted 8-10 membered bicyclic heteroaryl ring that has at least one nitrogen and 0-4 additional heteroatoms selected independently of nitrogen, oxygen or sulfur.
[095] In certain modalities, at least one of R3 and R4 is halogen. In some embodiments, none of R3 and R4 is halogen.
[096] In certain embodiments, R4 is -N (R) 2. In some embodiments, R4 is -N (R) 2 where each R is hydrogen. In some embodiments, R4 is -N (R) 2, where only one R is hydrogen. In some embodiments, R4 is -N (R) 2, where no R is hydrogen.
[097] In other embodiments, R4 is -N (R) 2, where the two groups R are taken together with nitrogen to form an optionally substituted 3-8 membered, partially unsaturated or aryl ring that has 0- 3 additional heteroatoms, not including the N atom of N (R) 2, selected independently of nitrogen, oxygen or sulfur, where R4 is coordinated with W by means of a nitrogen. In some embodiments, the two R groups are taken together with nitrogen to form an optionally substituted 5-membered heteroaryl ring that has 0-3 additional nitrogen atoms, not including the N atom of N (R) 2. Such rings include optionally substituted pyrrol-1-yl, pyrazol-1-yl, imidazol-1-yl and triazol-1-yl. In some embodiments, these rings are unsubstituted pyrrol-1-yl, pyrazol-1-yl, imidazol-1-yl and triazol-1-yl.
[098] In some embodiments, R4 is an optionally substituted 5-6 membered heteroaryl monocyclic ring that has at least one nitrogen and 0-3 additional heteroatoms selected independently of nitrogen, oxygen or sulfur. In some embodiments, R4 is an optionally substituted group selected from pyrrolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, isoxazolyl, oxadiazoyl, thiazolyl and thiazolyl. In some embodiments, R4 is an unsubstituted group selected from pyrrolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, isoxazolyl, oxadiazoyl, thiazolyl and thiazolyl. In some embodiments, R4 is a substituted group selected from pyrrolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, isoxazolyl, oxadiazoyl, thiazolyl and thiazolyl. In some embodiments, R4 is unsubstituted pyrrolyl. In some embodiments, R4 is substituted pyrrolyl.
[099] In other embodiments, R4 is an optionally substituted 8-10 membered bicyclic heteroaryl ring that has at least one nitrogen and 0-4 additional heteroatoms selected independently of nitrogen, oxygen or sulfur. In some embodiments, R4 is an optionally substituted group selected from indolyl, benzimidazolyl and indazolyl. In some embodiments, R4 is an unsubstituted group selected from indolyl, benzimidazolyl and indazolyl. In some embodiments, R4 is a substituted group selected from indolyl, benzimidazolyl and indazolyl.
[0100] In certain modalities, the hapticity of R4 is 1. In certain modalities, the hapticity of R4 is more than 1. In certain modalities, the hapticity of R4 is 2-8. In certain modalities, the hapticity of R4 is 2. In certain modalities, the hapticity of R4 is 3. In certain modalities, the hapticity of R4 is 4. In certain modalities, the hapticity of R4 is 5. In certain modalities, the hapticity of R4 is 6. In certain embodiments, the hapticity of R4 is 7. In certain embodiments, the hapticity of R4 is 8.
[0101] In certain embodiments, R4 is an optionally substituted group selected from:
where each represents the point of adhesion to the metal.
[0102] In some embodiments, R4 is -OR, where R is as defined above and described here. In some embodiments, R4 is -OR, where R is hydrogen. In some embodiments, R4 is -OR, where R is an optionally substituted group selected from C1-20 aliphatic, C1-20 heteroaliphatic that has 1-3 heteroatoms selected independently of nitrogen, oxygen or sulfur, phenyl, ferrocene, a carbocyclic ring saturated or partially unsaturated 3-7 membered, a saturated, partially unsaturated or aryl 8-10 membered bicyclic ring, a 5-6 membered heteroaryl monocyclic ring that has 14 heteroatoms independently selected from nitrogen, oxygen or sulfur, a heterocyclic ring saturated or partially unsaturated 4-7 member that has 1-3 heteroatoms selected independently of nitrogen, oxygen or sulfur, a saturated or partially unsaturated 7-10 membered bicyclic heterocyclic ring that has 1-5 heteroatoms selected regardless of nitrogen, oxygen or sulfur or an 8-10 membered bicyclic heteroaryl ring that has 1-5 heteroatoms selected independently of nitrogen oxygen, or sulfur. In some embodiments, R4 is -OR, where R is an optionally substituted aliphatic C1-20. In some embodiments, R4 is -OR, where R is an optionally substituted heteroaliphatic C1-20 that has 1-3 heteroatoms selected independently of nitrogen, oxygen or sulfur. In some embodiments, R4 is -OR, where R is an optionally substituted phenyl. In some embodiments, R4 is -OR, where R is an optionally substituted 3-7 membered saturated or partially unsaturated carbocyclic ring. In some embodiments, R4 is - OR, where R is a saturated, partially unsaturated or optionally substituted 8-10 membered aryl ring. In some embodiments, R4 is -OR, where R is an optionally substituted 5-6 membered heteroaryl monocyclic ring that has 1-4 heteroatoms selected independently of nitrogen, oxygen or sulfur. In some embodiments, R4 is -OR, where R is an optionally substituted 4-7 membered saturated or partially unsaturated heterocyclic ring that has 1-3 heteroatoms selected independently of nitrogen, oxygen or sulfur. In some embodiments, R4 is -OR, where R is an optionally substituted 7-10 membered saturated or partially unsaturated bicyclic heterocyclic ring that has 1-5 heteroatoms selected independently of nitrogen, oxygen or sulfur. In some embodiments, R4 is -OR, where R is an optionally substituted 8-14 membered bicyclic or tricyclic heteroaryl ring that has 1-5 heteroatoms selected independently of nitrogen, oxygen or sulfur.
[0103] In some embodiments, R4 is -OR, where R is an optionally substituted phenyl. In some embodiments, R4 is phenoxide. In certain embodiments, R4 is -OR, where R is a substituted phenyl. In certain embodiments, R4 is -OR, where R is a phenyl substituted with one or more optionally substituted alkyl groups. In certain embodiments, R4 is - OR, where R is 2,6-disubstituted phenyl with two optionally substituted alkyl substituents. In certain embodiments, R4 is -OR, where R is phenyl 2,4,6-tri-substituted with three optionally substituted alkyl substituents. In certain embodiments, R4 is -OR, where R is a phenyl substituted with one or more optionally substituted aryl groups. In certain embodiments, R4 is - OR, where R is 2,6-disubstituted phenyl with two optionally substituted aryl substituents. In certain embodiments, R4 is -OR, where R is phenyl 2,4,6-tri-substituted with three optionally substituted aryl substituents. In certain embodiments, R4 is -OR, where R is a phenyl substituted with one or more optionally substituted phenyl groups. In certain embodiments, R4 is - OR, where R is 2,6-disubstituted phenyl with two optionally substituted phenyl substituents. In certain embodiments, R4 is -OR, where R is phenyl 2,4,6-tri-substituted with three optionally substituted phenyl substituents. In certain embodiments R4 is O-2,6-dimesithylphenoxide (OHMT). In certain embodiments R4 is O-2,6- (2,4,6-triisopropylphenyl) 2C6H3 (OHIPT). In some embodiments, R4 is not -O-2,6-Ph2C6H3. In some embodiments, R4 is 2,6-pentafluorfenylphenoxide (DFTO or decafluorterphenoxide).
[0104] In some embodiments, R4 is an optionally substituted group selected from:
where each represents the point of adherence to W.
[0105] In other embodiments, -OR4 is an optionally substituted portion. In some embodiments, R3 is optionally replaced with one or more electron removal groups. In some embodiments, R3 is optionally substituted with one or more halogens. In some embodiments, R3 is optionally substituted with one or more - F. In some embodiments, R3 is optionally substituted with one or more -Cl. In some embodiments, R3 is optionally replaced with one or more -Br. In some embodiments, R3 is optionally replaced with one or more -I.
[0106] Exemplary R3 groups are revealed below,

[0107] Exemplary R4 groups are revealed below, with each representing the point of adhesion to the metal:

[0108] As generally defined above, n is 0, 1 or 2.
[0109] In some modalities, n is 0. In some modalities, n is 1. In some modalities, n is 2.
[0110] In certain embodiments, n is 0 and the present invention provides a compound of formula II:
II and described in modalities presented here, either alone or in combination.
[0111] In some embodiments, the present invention provides a compound of formula II-a, below:
wherein each of R1, R3 and R4 is as defined above and described in embodiments herein, either alone or in combination.
[0112] In certain embodiments, n is 1 and the present invention provides a compound of formula III:
wherein each of R1, R2, R3, R4 and R5 is as defined above and described in embodiments herein, either alone or in combination.
[0113] In some embodiments, the present invention provides a compound of formula III-a:
and described in modalities presented here, either alone or in combination.
[0114] In certain embodiments, n is 2 and the present invention provides a compound of formula IV:
wherein each of R1, R2, R3, R4 and R5 is as defined above and described in modalities, either alone or in combination.
[0115] In certain embodiments, the present invention provides a compound of formula IV-a:
wherein each of R1, R3, R4 and R5 is as defined above and described in embodiments herein, either alone or in combination.
[0116] As generally defined above, each R5 is independently a monodentate ligand, or two R5 are taken together with their intervening atoms to form an optionally substituted bidentate group. In some embodiments, each R5 is independently halogen, nitrogen-containing ligand, oxygen-containing ligand or phosphorus-containing ligand. In some embodiments, two R5s are taken together with their intervening atoms to form an optionally substituted bidentate group. Those skilled in the art will note that R5 can be any suitable ligand capable of coordination with W. In some embodiments, these ligands are disclosed here.
[0117] In certain embodiments, the hapticity of R5 is 1. In certain embodiments, the hapticity of R5 is more than 1. In certain embodiments, the hapticity of R5 is 2-8. In certain modalities, the hapticity of R5 is 2. In certain modalities, the hapticity of R5 is 3. In certain modalities, the hapticity of R5 is 4. In certain modalities, the hapticity of R5 is 5. In certain modalities, the hapticity of R5 is 6. In certain embodiments, the hapticity of R5 is 7. In certain embodiments, the hapticity of R5 is 8.
[0118] In some embodiments, each R5 is independently a nitrogen-containing ligand capable of coordinating with W via the nitrogen atom. Consequently, in some embodiments, each R5 is independently -N (R) 2, -NRC (O) R, -NRC (O) OR, - NRC (O) N (R) 2, -NRSO2R, - NRSO2N (R) 2, -NROR, N (R) 3, a 5-6 membered heteroaryl monocyclic ring that has at least one nitrogen atom and 0-3 additional heteroatoms selected independently of nitrogen, oxygen or sulfur, a saturated or partially unsaturated heterocyclic ring 4-7 member that has at least one nitrogen atom and 0-2 additional hetero atoms independently selected from nitrogen, oxygen or sulfur, a 7-10 membered saturated or partially unsaturated bicyclic heterocyclic ring that has at least one nitrogen atom and 0-4 additional heteroatoms selected independently of nitrogen, oxygen or sulfur or an 8-14 membered bicyclic or tricyclic heteroaryl ring that has at least one nitrogen atom and 0-4 additional heteroatoms selected independently of nitrogen, oxygen or sulfur or two R5 are tone together with their intervening atoms to form an optionally substituted bidentate group, each R being independently as defined above or described herein.
[0119] In some embodiments, at least one of R5 is independently selected from an optionally substituted 6-membered heteroaryl ring that has 1-3 nitrogens. This R5 includes optionally substituted pyridine, pyrimidine or triazine groups.
[0120] In certain embodiments, each R5 is independently optionally substituted pyridine. In some embodiments, each R5 is independently optionally substituted pyridine.
[0121] In other modalities, each R5 is selected independently from an optionally substituted 5-membered heteroaryl ring that has one nitrogen and 0-2 additional heteroatoms selected independently from nitrogen, oxygen or sulfur. These R5 groups include optionally substituted pyrrole, pyrazole, imidazole, triazole, oxazole, isoxazole, oxadiazole, thiazole and thiadiazole rings.
[0122] In some embodiments, at least one of R5 is independently -N (R) 2, -NHC (O) R, - NHC (O) OR, - NHC (O) N (R) 2, N (R) 3 or -NHSO2R, where each R is independently as defined above or described herein. In some embodiments, at least one of R5 is -N (R) 2, where each R is independently as defined above or described herein.
[0123] In certain embodiments, each R5 is independently -N (R) 2, where each R is independently hydrogen or an optionally substituted group selected from C1-20 aliphatic, phenyl, a 3-7 saturated or partially unsaturated carbocyclic ring members, a saturated, partially unsaturated or aryl 8-10 membered bicyclic ring, a 5-6 membered heteroaryl monocyclic ring having 1-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, a saturated or partially unsaturated heterocyclic ring of 4 -7 members having 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, a 7-10 membered saturated or partially unsaturated bicyclic heterocyclic ring having 1-5 heteroatoms independently selected from nitrogen, oxygen or sulfur or a bicyclic heteroaryl ring or 8-14 membered tricyclic that has 1-5 heteroatoms selected independently of nitrogen, oxygen or sulfur. In some embodiments, one group R is hydrogen and the other is an optionally substituted group selected from phenyl, naphthyl, cyclohexyl, pyridyl, pyrimidinyl, cyclopentyl, methyl, ethyl, propyl or butyl.
[0124] In certain embodiments, each R5 is independently -N (R) 2, where the two R groups are taken together with the nitrogen atom to form an optionally substituted 3-8 membered, partially unsaturated or aryl ring which has 0-3 additional heteroatoms, not including the N atom of N (R) 2, selected independently of nitrogen, oxygen or sulfur. In some embodiments, the two R groups are taken together with nitrogen to form an optionally substituted 5-membered heteroaryl ring that has 1-3 nitrogen atoms. Such rings include optionally substituted pyrrol-1-yl, pyrazol-1-yl, imidazol-1-yl and triazol-1-yl.
[0125] In certain embodiments, each R5 is independently N (R) 3, where each R is independently as defined above or described herein. In certain embodiments, each R5 is independently N (R) 3, where each R is independently hydrogen or an optionally substituted group selected from C1-20 aliphatic, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, a ring saturated, partially unsaturated or 8-10 membered aryl bicyclic, a 5-6 membered heteroaryl monocyclic ring having 1-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, a 4-7 membered saturated or partially unsaturated heterocyclic ring that it has 1-3 heteroatoms selected independently of nitrogen, oxygen or sulfur, a 7-10 membered saturated or partially unsaturated bicyclic heterocyclic ring which has 1-5 heteroatoms selected independently of nitrogen, oxygen or sulfur or an 8-bicyclic or tricyclic heteroaryl ring -14 members that have 1-5 heteroatoms selected independently of nitrogen, oxygen or sulfur. In some embodiments, one group R is hydrogen and the other is an optionally substituted group selected from phenyl, naphthyl, cyclohexyl, pyridyl, pyrimidinyl, cyclopentyl, methyl, ethyl, propyl or butyl.
[0126] In certain embodiments, each R5 is independently N (R) 3, where the two or three R groups are taken together with the nitrogen atom to form an optionally saturated, partially unsaturated or 3-12 membered aryl substituted that has 0-5 additional hetero atoms, not including the N atom of N (R) 3, selected independently of nitrogen, oxygen or sulfur. In some embodiments, two or three R groups are taken together with nitrogen to form an optionally substituted 5-membered heteroaryl ring that has 1-3 nitrogen atoms. These rings include optionally substituted pyrrole, pyrazole, imidazole and triazole.
[0127] In certain embodiments, each R5 is independently -NHC (O) R, where R is as defined above or described herein. In some embodiments, each R5 is independently -NHC (O) R, where R is an optionally substituted group selected from C1-20 aliphatic, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, a saturated bicyclic ring, partially unsaturated or 8-10 membered aryl, a 5-6 membered heteroaryl monocyclic ring having 1-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, a 4-7 membered saturated or partially unsaturated heterocyclic ring having 1- 3 heteroatoms selected independently of nitrogen, oxygen or sulfur, a 7-10 membered saturated or partially unsaturated bicyclic heterocyclic ring having 1-5 heteroatoms selected independently of nitrogen, oxygen or sulfur or an 8-14 membered bicyclic or tricyclic heteroaryl ring which has 1-5 heteroatoms selected independently of nitrogen, oxygen or sulfur. In some embodiments, R is an optionally substituted group selected from phenyl, naphthyl, cyclohexyl, pyridyl, pyrimidinyl, cyclopentyl, methyl, ethyl, propyl or butyl.
[0128] In some embodiments, two R5s are taken together with their intervening atoms to form an optionally substituted bidentate portion. In certain embodiments, two R5's are taken together to form optionally substituted bipyridyl. In certain modalities, two R5s are taken together to form:

[0129] In some embodiments, two R5s are taken together with their intervening atoms to form an optionally substituted bicyclic or tricyclic heteroaryl ring that has 1-3 heteroatoms selected independently of nitrogen, oxygen or sulfur. In certain embodiments, two R5's are taken together to form optionally substituted phenanthroline. In certain modalities, two R5s are taken together to form:

[0130] In some embodiments, each R5 is independently a binder that contains oxygen. In some embodiments, each R5 is independently an oxygen-containing ligand capable of coordinating with W via the oxygen atom. In some embodiments, each R5 is independently -OR, O (R) 2, a 5-6 membered heteroaryl monocyclic ring that has at least one oxygen atom and 0-3 additional heteroatoms selected independently of nitrogen, oxygen or sulfur, a 4-7 membered saturated or partially unsaturated heterocyclic ring that has at least one oxygen atom and 02 additional heteroatoms selected independently of nitrogen, oxygen or sulfur, a 7-10 membered saturated or partially unsaturated bicyclic ring that has at least one oxygen atom and 0-4 additional heteroatoms selected independently of nitrogen, oxygen or sulfur or an 8-14 membered bicyclic or tricyclic heteroaryl ring that has at least one oxygen atom and 0-4 additional heteroatoms selected independently of nitrogen, oxygen or sulfur or two R5 are taken together with their intervening atoms to form an optionally sub-bidentate group constituted, where each R is independently as defined above or described herein.
[0131] In certain embodiments, each R5 is independently -OR, where each R is independently as defined above or described herein. In certain embodiments, each R5 is independently -OR, where each R is independently hydrogen or an optionally substituted group selected from C1-20 aliphatic, phenyl, ferrocene, a 3-7 membered saturated or partially unsaturated carbocyclic ring, a bicyclic ring saturated, partially unsaturated or 8-10 membered aryl, a 5-6 membered heteroaryl monocyclic ring that has 1-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, a 4-7 membered saturated or partially unsaturated heterocyclic ring that has 1-3 heteroatoms selected independently of nitrogen, oxygen or sulfur, a 7-10 membered saturated or partially unsaturated bicyclic heterocyclic ring having 1-5 heteroatoms independently selected from nitrogen, oxygen or sulfur or an 8- bicyclic or tricyclic heteroaryl ring 14 members that have 1-5 heteroatoms selected independently of nitrogen, oxygen or sulfur. In some embodiments, one group R is hydrogen and the other is an optionally substituted group selected from phenyl, naphthyl, cyclohexyl, pyridyl, pyrimidinyl, cyclopentyl, methyl, ethyl, propyl or butyl.
[0132] In certain embodiments, each R5 is independently O (R) 2, where each R is independently as defined above or described herein. In certain embodiments, each R5 is independently O (R) 2, where each R is independently hydrogen or an optionally substituted group selected from C1-20 aliphatic, phenyl, ferrocene, a 3-7 membered saturated or partially unsaturated carbocyclic ring, an 8-10 membered saturated, partially unsaturated or aryl bicyclic ring, a 5-6 membered heteroaryl monocyclic ring having 1-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, a 4-7 saturated or partially unsaturated heterocyclic ring members having 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, a 7-10 membered saturated or partially unsaturated bicyclic heterocyclic ring having 1-5 heteroatoms independently selected from nitrogen, oxygen or sulfur or a bicyclic or tricyclic heteroaryl ring 8-14 members with 1-5 heteroatoms selected independently of nitrogen, oxygen or sulfur. In some embodiments, one group R is hydrogen and the other is an optionally substituted group selected from phenyl, naphthyl, cyclohexyl, pyridyl, pyrimidinyl, cyclopentyl, methyl, ethyl, propyl or butyl.
[0133] In certain embodiments, each R5 is independently O (R) 2, in which the two R groups are taken together with the oxygen atom to form an optionally substituted 3-8 membered saturated, partially unsaturated or aryl ring that it has 0-3 additional heteroatoms, not including the oxygen atom of O (R) 2, selected independently of nitrogen, oxygen or sulfur.
[0134] In some embodiments, each R5 is independently a binder containing phosphorus. In some embodiments, each R5 is independently a phosphorus-containing ligand capable of coordinating with W via the phosphorus atom. In some embodiments, each R5 is independently -P (R ') 2, P (R') 3, -P (O) (R ') 2, P (O) (R') 3, where: each R ' is independently halogen, -R, -OR, - N (R) 2, or two or three R 'are taken together with the phosphorus to form a 3-20 membered ring optionally substituted with 0-10 additional hetero atoms, not including the phosphorus atom of -P (R ') 2, P (R') 3, -P (O) (R ') 2 or P (O) (R') 3, independently selected from nitrogen, oxygen, sulfur or phosphor; and each R is independently hydrogen or an optionally substituted group selected from C1-20 aliphatic, C120 heteroaliphatic having 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, phenyl, ferrocene, a 3-7 saturated or partially unsaturated carbocyclic ring a 8-10 membered saturated, partially unsaturated or aryl 8-10 membered bicyclic ring, a 5-6 membered heteroaryl monocyclic ring having 14 heteroatoms independently selected from nitrogen, oxygen or sulfur, a 4-7 saturated or partially unsaturated heterocyclic ring members having 1-3 hetero atoms independently selected from nitrogen, oxygen or sulfur, a 7-10 membered saturated or partially unsaturated bicyclic heterocyclic ring having 1-5 hetero atoms independently selected from nitrogen, oxygen or sulfur or an 8-membered bicyclic heteroaryl ring -10 members that have 1-5 heteroatoms selected independently of nitrogen , oxygen or sulfur, or: two R groups on the same nitrogen atom are taken together with nitrogen to form an optionally substituted 3-12 membered saturated, partially unsaturated or aryl ring that has 0-5 additional hetero atoms, not including the same nitrogen atom, independently selected from nitrogen, oxygen or sulfur; or: two R groups on the same oxygen atom are taken together with oxygen to form an optionally substituted saturated, partially unsaturated or 3-12 membered aryl ring that has 0-5 additional heteroatoms, not including the same oxygen atom, independently of nitrogen, oxygen or sulfur.
[0135] In some embodiments, each R5 is independently P (R ') 3, where each R' is independently as defined above and described herein. In some embodiments, each R5 is independently P (R ') 3, where each R' is R and where R is as defined above and described herein. In some embodiments, each R5 is independently P (R ') 3, where each R' is an optionally substituted group selected from hydrogen, aliphatic C1-20, phenyl or ferrocene.
[0136] In some modalities, one or two R5 are partially dissociated.
[0137] Exemplary monodentate and bidentate R5 groups are revealed below:

[0138] In some embodiments, two or more of R1, R2, R3, R4 and R5 can be taken together with their intervening atoms to form an optionally substituted polyidentated ligand. In some embodiments, two or more of R1, R3, R4 and R5 can be taken together with their intervening atoms to form an optionally substituted polyidentated ligand. In some embodiments, two or more of R1, R2, R3 and R4 can be taken together with their intervening atoms to form an optionally substituted polyidentated ligand. In some embodiments, two or more of R3, R4 and R5 can be taken together with their intervening atoms to form an optionally substituted polyidentated ligand. In some embodiments, R3 and R4 are taken together with their intervening atoms to form an optionally substituted polyidentate ligand.
[0139] As defined above, each R is independently hydrogen or an optionally substituted group selected from C1-20 aliphatic, C1-20 heteroaliphatic having 1-3 heteroatoms selected independently from nitrogen, oxygen or sulfur, phenyl, ferrocene, a ring 3-7 membered saturated or partially unsaturated carbocyclic, 8-10 membered saturated, partially unsaturated or aryl bicyclic ring, 5-6 membered heteroaryl monocyclic ring that has 14 heteroatoms selected independently of nitrogen, oxygen or sulfur, a ring 4-7 membered saturated or partially unsaturated heterocyclic having 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, a 7-10 membered saturated or partially unsaturated heterocyclic ring having 1-5 heteroatoms independently selected from nitrogen, oxygen or sulfur or an 8-10 membered bicyclic heteroaryl ring that has 1-5 heteroatoms selects independently of nitrogen, oxygen or sulfur, or: two or three R groups on the same nitrogen atom are taken together with nitrogen to form an optionally substituted 3-12 membered saturated, partially unsaturated or aryl ring that has 0-5 additional hetero atoms, not including the same nitrogen atom, selected independently of nitrogen, oxygen or sulfur; or: two R groups on the same oxygen atom are taken together with oxygen to form an optionally substituted saturated, partially unsaturated or 3-12 membered aryl ring that has 0-5 additional heteroatoms, not including the same oxygen atom, independently of nitrogen, oxygen or sulfur.
[0140] In some modalities, R is hydrogen. In some embodiments, R is not hydrogen.
[0141] In some embodiments, R is optionally substituted aliphatic C1-20. In some modalities, R is C1-20 heteroaliphatic which has 1-3 heteroatoms selected independently of nitrogen, oxygen or sulfur. In some embodiments, R is an optionally substituted 3-7 membered saturated or partially unsaturated carbocyclic ring. In some embodiments, R is an 8-10 membered optionally substituted saturated or partially unsaturated bicyclic ring. In some embodiments, R is an optionally substituted 4-7 membered saturated or partially unsaturated heterocyclic ring that has 1-3 heteroatoms selected independently of nitrogen, oxygen or sulfur. In some embodiments, R is a 7-10 membered optionally substituted saturated or partially unsaturated bicyclic heterocyclic ring that has 1-5 heteroatoms selected independently of nitrogen, oxygen or sulfur.
[0142] In some embodiments, R is independently an optionally substituted group selected from phenyl, an 8-10 membered aryl bicyclic ring, a 5-6 membered heteroaryl monocyclic ring that has 1-4 heteroatoms selected independently of nitrogen, oxygen or sulfur or an 8-10 membered bicyclic heteroaryl ring that has 1-5 heteroatoms selected independently of nitrogen, oxygen or sulfur.
[0143] In some embodiments, R is optionally substituted phenyl. In some embodiments, R is phenyl substituted with one or more optionally substituted alkyl groups. In some embodiments, R is 2,6-disubstituted phenyl with two optionally substituted alkyl substituents. In some embodiments, R is phenyl 2,4,6-trisubstituted with three optionally substituted alkyl substituents. In some embodiments, R is a phenyl substituted with one or more optionally substituted aryl groups. In some embodiments, R is a phenyl substituted with one or more optionally substituted phenyl groups. In some embodiments, R is phenyl 2,6-disubstituted with two optionally substituted aryl substituents. In some embodiments, R is phenyl 2,4,6-tri-substituted with three optionally substituted aryl substituents. In some embodiments, R is a phenyl substituted with one or more optionally substituted phenyl groups. In some embodiments, R is phenyl 2,6-disubstituted with two optionally substituted phenyl substituents. In some embodiments, R is phenyl 2,4,6-tri-substituted with three optionally substituted phenyl substituents.
[0144] In some modalities, R is
optionally replaced. In some embodiments, R is optionally substituted with one or more electron withdrawal groups. In some embodiments, R is optionally substituted with one or more halogens. In some embodiments, R is optionally substituted with one or more - F. In some embodiments, R is optionally substituted with one or more -Cl. In some embodiments, R is optionally substituted with one or more -Br. In some embodiments, R is optionally substituted with one or more - I. In some embodiments, R is 2,6-dimesithylphenyl (HMT). In some embodiments, R is 2,6- (2,4,6-triisopropylphenyl) 2C6H3 (HIPT).
[0145] In some modalities, R is 2,6-pentafluorfenylphenoxide (DFT).
[0146] In some embodiments, R is an 8-10 membered aryl ring optionally substituted. In some embodiments, R is a 5-6 membered heteroaryl monocyclic ring that has 1-4 heteroatoms selected independently of nitrogen, oxygen or sulfur. In some embodiments, R is an optionally substituted 810-membered bicyclic heteroaryl ring that has 1-5 heteroatoms selected independently of nitrogen, oxygen or sulfur.
[0147] In some modalities, R is an optionally substituted group selected from:
Exemplary optional substituents, as described above, include, without limitation, alkyl, halogen, groups - OSiR3.
[0148] In some embodiments, two or three R groups on the same nitrogen atom are taken together with nitrogen to form a saturated, partially unsaturated or optionally substituted 3-12 membered aryl ring that has 0-5 additional hetero atoms, not including the same nitrogen atom, independently selected from nitrogen, oxygen or sulfur. In some embodiments, two R groups on the same nitrogen atom are taken together with nitrogen to form an optionally substituted 3-12 membered saturated, partially unsaturated or aryl ring that has 0-5 additional hetero atoms, not including the same atom nitrogen, independently selected from nitrogen, oxygen or sulfur. In some embodiments, two R groups on the same oxygen atom are taken together with oxygen to form an optionally substituted saturated, partially unsaturated or 3-12 membered aryl ring that has 0-5 additional hetero atoms, not including the same atom oxygen, independently selected from nitrogen, oxygen or sulfur. In some embodiments, two R groups are taken together with nitrogen to form an optionally substituted 5-membered heteroaryl ring that has 0-3 additional nitrogen atoms, not including the N of - N (R) 2 atom. Such rings include optionally substituted pyrrol-1-yl, pyrazol-1-yl, imidazol-1-yl and triazol-1-yl. In some embodiments, these rings are unsubstituted pyrrol-1-yl, pyrazol-1-yl, imidazol-1-yl and triazol-1-yl.
[0149] More modalities of R include, without limitation, those described in the modalities of R1, R2, R3, 4 5 6 7 8 9 10 11 12 R, R, R, R, R, R, R, R and R.
[0150] Exemplary compounds of formula I are shown in Table 1, below. Table 1. Exemplary compounds.


[0151] In some embodiments, the present invention provides a compound of formula V:
where: each of R6 and R7 is independently halogen, -OR or a phosphorus-containing binder; each R8 is independently a monodentate ligand, or two R8 are taken together with their intervening atoms to form an optionally substituted bidentate group; and each of R1, R2 and n is independently as defined above and described herein.
[0152] In some modalities, n = 2.
[0153] In some embodiments, R8 is independently a monodentate ligand, or two R8 are taken together with their intervening atoms to form an optionally substituted bidentate group. In some embodiments, R8 is R5, where R5 is as defined above and described herein.
[0154] In some embodiments, each of R6 R7 and R8 is independently selected from halogen and P (R ') 3, where each R' is independently as defined above or described herein. In some embodiments, each of R6 and R7 is independently halogen and each of R8 is independently P (R ') 3-. In some embodiments, n = 2, each of R6 and R7 is independently halogen, and each of R8 is independently P (R ') 3. In some embodiments, each of R6 and R7 is independently halogen, n is 2 and R8 is PR3, where each of R is independently as defined above and described herein.
[0155] In some embodiments, a compound of formula V is WO (CHR1R2) (P (R) 3) 2Cl2 or WO (CHR1R2) (P (R) 3) 2Br2, where each of R1 and R2 is independently as defined above or described herein, and each R is independently an optionally substituted group selected from C1-20 aliphatic or phenyl. In some embodiments, a compound of formula V is WO (CH-t-Bu) (PMe2Ph) 2Cl2. In some embodiments, a compound of formula V is WO (CH-t-Bu) (PMe3) 2Cl2. In some embodiments, a compound of formula V is W (O) (CH-t-Bu) (OHMT) (PMe2Ph) Cl. In some embodiments, a compound of formula V is W (O) (CH-t-Bu) (OHIPT) (PMe2Ph) Cl. In some embodiments, a compound of formula V is W (O) (CH-t-Bu) (DFTO) (PMe2Ph) Cl.
[0156] In some embodiments, a compound of formula V has the structure of formula Va:
where: each of R9 and R10 is independently halogen; and each of R1, R2, R8 and n is independently as defined above and described herein.
[0157] In some modalities, R9 is -F. In some embodiments, R9 is -Cl. In some modalities, R9 is -Br. In some embodiments, R9 is -I. In some embodiments, R10 is -F. In some embodiments, R10 is -Cl. In some modalities, R10 is -Br. In some embodiments, R10 is -I.
[0158] In some modalities, both R9 and R10 are -Cl. In some embodiments, n = 2 and both R8 are monodentated phosphine ligands. In some embodiments, n = 2 and both R8 are monodentate phosphine linkers having the structure of PR3, each of R is independently as defined above and described herein. In some embodiments, two R8's are taken together to form a bidentate phosphine ligand.
[0159] In some embodiments, a compound of structure V or Va has the structure of W (O) (CHR1) Cl2 (R8) 2, where R8 is a monodentate phosphine ligand that has the structure of PR3, in which each R is independently as defined above and described herein. In some modalities, PR3 is PMe2Ph. In some embodiments, a compound of structure V or V-a is W (O) (CHt-Bu) Cl2 (PMe2Ph) 2. In some embodiments, a compound of structure V or V-a is W (O) (CHCMe2Ph) Cl2 (PMe2Ph) 2.
[0160] In some embodiments, the present invention provides a compound of formula V that has the structure of formula Vb:
where: R11 is -OR; and each of R1, R2, R8, R9, R10, R and n is independently as defined above and described herein.
[0161] -OR exemplary for R11 is intensively described in the specification, for example, without limitation, the modalities described for R3 and R4. In some embodiments, R11 is -OR, where R is not hydrogen. In some embodiments, R11 is -OR, where R is an optionally substituted group selected from C1-20 aliphatic or phenyl. In certain embodiments, R11 is -OR, where R is optionally substituted phenyl. In certain embodiments, R11 is - OR, where R is substituted phenyl. In certain embodiments, R11 is -OR, where R is phenyl substituted with one or more optionally substituted alkyl groups. In certain embodiments, R11 is -OR, where R is 2,6-disubstituted phenyl with two optionally substituted alkyl substituents. In certain embodiments, R11 is -OR, where R is phenyl 2,4,6-tri-substituted with three optionally substituted alkyl substituents. In certain embodiments, R11 is - OR, where R is a phenyl substituted with one or more optionally substituted aryl groups. In certain embodiments, R11 is -OR, where R is 2,6-disubstituted phenyl with two optionally substituted aryl substituents. In certain embodiments, R11 is -OR, where R is phenyl 2,4,6-tri-substituted with three optionally substituted aryl substituents. In certain embodiments, R11 is - OR, where R is a phenyl substituted with one or more optionally substituted phenyl groups. In certain embodiments, R11 is -OR, where R is 2,6-disubstituted phenyl with two optionally substituted phenyl substituents. In certain embodiments, R11 is -OR, where R is phenyl 2,4,6-tri-substituted with three optionally substituted phenyl substituents. In certain embodiments R11 is O-2,6-dimesithylphenoxide (OHMT). In certain embodiments, R11 is O-2,6- (2,4,6-triisopropylphenyl) 2C6H3 (OHIPT). In certain embodiments, R11 is 2,6-pentafluorfenylphenoxide (DFTO or decafluorterphenoxide). In some embodiments, -OR is -OHMT. In some modalities, -OR is OHIPT. In some modalities, -OR is DFTO. In some embodiments, at least one of R3 and R4 is not -O-2,6-Ph2C6H3.
[0162] In some embodiments, a compound of formula V-b is W (O) (CH-t-Bu) (OHMT) (PMe2Ph) Cl. In some embodiments, a compound of formula V-b is W (O) (CH-t-Bu) (OHIPT) (PMe2Ph) Cl. In some embodiments, a compound of formula V-b is W (O) (CH-t-Bu) (DFTO) (PMe2Ph) Cl.
[0163] In some embodiments, the present invention provides a compound of formula VI:
wherein each of R1, R2, n and R5 is independently as defined above and described herein. In some embodiments, the two R1 in formula VI are the same. In some embodiments, the two R2 in formula VI are the same. In some embodiments, the two R1 in formula VI are the same and the two R2 in formula VI are the same.
[0164] In some embodiments, a compound of formula VI has the structure of formula VI-a:
wherein each of R1, n, and R5 is independently as defined above and described herein. In some embodiments, the two R1 in formula VI-a are the same.
[0165] In some embodiments, each R1 in formula VI or VI-a is R. In some embodiments, each R1 in formula VI or VI-a is optionally substituted aliphatic C1-20. In some embodiments, each R1 in formula VI or VI-a is optionally substituted with tert-butyl.
[0166] In some embodiments, each R5 in formula VI or VI-a is independently a monodentate ligand. In some embodiments, each R5 in formula VI or VI-a is independently a monodentate binder containing nitrogen. In some embodiments, each R5 in formula VI or VI-a is independently a monodentate linker that contains phosphorus.
[0167] In some embodiments, two R5 in formula VI-a are taken together with their intervening atoms to form an optionally substituted bidentate portion. In certain embodiments, two R5's are taken together to form an optionally substituted bidentate bipyridyl.
[0168] In some embodiments, a compound of formula VI is WO (CH2t-Bu) (beep) (beep = 2,2'-pyridine). In some embodiments, a compound of formula VI is WO (CH2CMe2Ph) (beep) (beep = 2,2'-pyridine).
[0169] In some embodiments, the present invention provides a compound of formula VII:
wherein each R9 is independently as defined above and described herein. In some embodiments, a compound of formula VII is W (O) 2 (Cl) 2 (beep). In some embodiments, a compound of formula VII is W (O) 2 (Br) 2 (beep).
[0170] In some embodiments, the present invention provides a compound of formula VIII:
where: R12 is -OR or -OSiR3; and each of R1, R2, R8, R11, R and n is independently as defined above and described herein. In some embodiments, a compound of formula VIII is different from WO (CH-t-Bu) (O-2,6-Ph2C6H3) 2 (R8) n. In some embodiments, at least one of R11 and R12 is not -O-2,6-Ph2C6H3. In some modalities, n = 0. In some modalities, n = 1.
[0171] In some embodiments, the present invention provides a compound of formula VIII-a
, where R11 is -OR; each of R1, R2, R8, R11, R and n is independently as defined above and described herein. In some modalities, both R11 and R11 are the same. In some modalities, R11 and R11 are different. Exemplary modalities of -OR for R11 and R11 are intensively described here above including, without limitation, those described for R3 and R4. In some embodiments, at least one of R11 and R11 is not -O-2,6-Ph2C6H3. In some embodiments, a compound of formula VIII-a is different from WO (CH-t-Bu) (O-2,6-Ph2C6H3) 2 (R8) n. In some modalities, n = 0. In some modalities, n = 1.
[0172] In some embodiments, a compound of formula VIII-a is W (O) (CH-t-Bu) (OHMT) 2. In some embodiments, a compound of formula VIII-a is W (O) (CH2) (OHMT) 2. In some embodiments, a compound of formula VIII-a is W (O) (CH2) (DFTO) 2.
[0173] In some embodiments, the present invention provides a compound of formula VIII-b:
wherein R is -OSiR3, and each of R1, R2, R8, R11, R and n is independently as defined above and described herein. In some modalities, n = 0.
[0174] In some embodiments, R12 is -OSiR3, where at least one R is not hydrogen. In some embodiments, R12 is -OSiR3, where at least two R's are not hydrogen. In some embodiments, R12 is -OSiR3, where none of R is hydrogen. In some embodiments, R12 is -OSiR3, where each R is independently an optionally substituted group selected from C1-20 aliphatic and phenyl. In some embodiments, R12 is -OSiR3, where at least one R is optionally substituted aliphatic C1-20. In some embodiments, R12 is -OSiR3, where at least one R is optionally substituted phenyl. In some modalities, R12 is - OSi (t-Bu) 3. In some embodiments, a compound of formula VIII-b is WO (CH-t-Bu) [OSi (t-Bu) 3] (OHMT). In some embodiments, a compound of formula VIII-b is WO (CH-t-Bu) [OSi (t-Bu) 3] (OHIPT). In some embodiments, a compound of formula VIII-b is WO (CH-t-Bu) [OSi (t-Bu) 3] (DFTO).
[0175] In some embodiments, a compound of formula VIII is W (O) (CH-t-Bu) (OHMT) 2. In some embodiments, a compound of formula VIII is W (O) (CH2) (OHMT) 2. In some embodiments, a compound of formula VIII is WO (CH-t-Bu) [OSi (t-Bu) 3] (OHMT). In some embodiments, a compound of formula VIII-b is WO (CH-t-Bu) [OSi (t-Bu) 3] (OHIPT). In some embodiments, a compound of formula VIII-b is WO (CH-t-Bu) [OSi (t-Bu) 3] (DFTO).
[0176] In some embodiments, the present invention provides a compound of formula IX:
where: R1 'and R2' are taken together with W to form an optionally substituted saturated or partially unsaturated 3-8 membered ring that has, in addition to the intervening metal atom, 0-4 heteroatoms selected independently of nitrogen, oxygen or sulfur; R3 'is R3 or -OSiR3; and each of R3, R4, R5 and n is independently as defined above and described herein.
[0177] In some embodiments, R1 and R2 are taken together with W to form an optionally substituted 4-membered metallacyclobutane. In some embodiments, R1 and R2 are taken together with W to form a substituted 4-membered metalacyclobutane. In some embodiments, R1 and R2 are taken together with W to form an unsubstituted 4-membered metalacyclobutane.
[0178] In some embodiments, R3 is R3, where R3 is as defined above and described here. In some embodiments, R3 is -OSiR3, where each R is independently as defined above and described herein. In some embodiments, R3 is -OSiR3, where at least one R is not hydrogen. In some embodiments, R3 is -OSiR3, where at least two R's are not hydrogen. In some embodiments, R3 is -OSiR3, where none of R is hydrogen. In some embodiments, R3 is -OSiR3, where at least one R is optionally substituted aliphatic C1-20. In some embodiments, R3 is -OSiR3, where at least one R is optionally substituted phenyl. In some modalities, R3 is - OSi (t-Bu) 3.
[0179] In some embodiments, R3 is -OR, where R is optionally substituted phenyl; or R3 'is -OSiR3. In some embodiments, R3 is -OR, where R is optionally substituted phenyl; or R3 is -OSiR3, where each R is independently C1-20 aliphatic or optionally substituted phenyl.
[0180] In some embodiments, R3 'is not -O-2,6- Ph2C6H3.
[0181] In some embodiments, each of R3 and R4 is independently -OR, where R is independently optionally substituted phenyl. In some embodiments, R3 is - OSiR3, where each R is independently C1-20 aliphatic or optionally substituted phenyl; and R4 is -OR, where R is optionally substituted phenyl. In some embodiments, R3 is -OR, where R is optionally substituted phenyl; or R3 is -OSiR3, where each R is independently C1-20 aliphatic or optionally substituted phenyl.
[0182] In some embodiments, a compound of formula IX is W (O) (CH2CH2CH2) (OHMT) (Silox) (Silox = -OSi (t-Bu) 3). In some embodiments, a compound of formula IX is W (O) (C3H6) (OHMT) 2. In some embodiments, a compound of formula IX is W (O) (C3H6) (OHIPT) 2. In some embodiments, a compound of formula IX is W (O) (C3H6) (DFTO) 2.
[0183] In some embodiments, the present invention provides new ligands and their protonated compounds or salts thereof. In some embodiments, the present invention provides methods for preparing new ligands and their protonated compounds or salts thereof. In some embodiments, a new ligand is 2,6-pentafluorfenylphenoxide (DFTO or decafluorterphenoxide). In some embodiments, a protonated compound of DFTO is DFTOH. In some embodiments, a DFTO salt is LiODFT. In some embodiments, the present invention provides a method for preparing DFTOH or its salts.
[0184] A new binder provided can be used to prepare a new compound or metal complexes. In some embodiments, the present invention provides a metal compound or complex that comprises a new binder. In some embodiments, the present invention provides a metal compound or complex that comprises one or more DFTO binders. In some embodiments, the present invention provides a metal compound or complex that comprises one or more DFTOH binders. In some embodiments, the present invention provides a compound having the structure of formula I, II, III, IV, V, VI, VII, VIII or IX, and which comprises one or more DFTO ligands. In some embodiments, the present invention provides a compound having the structure of formula I, II, III, IV, V, VI, VII, VIII or IX, and which comprise one or more DFTOH ligands.
[0185] In some embodiments, a compound disclosed in that invention forms a complex with a Lewis acid. In some embodiments, a Lewis acid comprises a boron atom. In some embodiments, a Lewis acid is of the structure of B (R ') 3. In some embodiments, a Lewis acid is of the structure of B (R) 3. In some embodiments, a Lewis acid is of the structure of B (R) 3, where R is not hydrogen. In some embodiments, a Lewis acid is of the structure of B (R) 3, where R is an optionally substituted C1-20 aliphatic or phenyl. In some embodiments, a Lewis acid is of the structure of B (R) 3, where R is an optionally substituted phenyl. In some embodiments, a Lewis acid is B (C6F5) 3.
[0186] In some embodiments, the present invention provides a compound that has the structure of any of the formulas described herein, wherein the compound is an oxo-tungsten-alkylidene 14e complex. In some embodiments, the present invention provides a compound having the structure of any of the formulas described herein, wherein the compound is an oxo-tungsten-alkylidene 14e complex and the complex is a syn isomer. In some embodiments, the present invention provides a compound having the structure of any of the formulas described herein, wherein the compound is an oxo-tungsten-alkylidene 16e complex.
[0187] In some embodiments, the present invention provides a compound that has the structure of any of the formulas described herein, wherein at least one linker is an optionally substituted phenoxide. In some embodiments, the present invention provides a compound that has the structure of any of the formulas described herein, wherein at least one linker is an optionally substituted 2,6-terphenoxide. In some embodiments, an optionally substituted 2,6-terphenoxide is OHMT. In some embodiments, an optionally substituted 2,6-terfenoxide is OHIPT. In some embodiments, an optionally substituted 2,6-terphenoxide is DFTO. In some embodiments, such a compound has good stability. In some embodiments, the optionally substituted 2,6-terphenoxide binder contributes to decrease the composition. In some embodiments, the optionally substituted 2,6-terphenoxide linker contributes to decreasing the bimolecular composition. COMPOUND PRODUCTION METHODS
[0188] The present invention recognizes the importance of improved methods for the preparation of oxo-tungsten-alkylidene complexes. It was known in the art that it is a challenge to produce relatively stable and reactive versions of oxo-tungsten-alkylidene complexes in good performance.
[0189] In certain embodiments, the present invention further provides methods of producing supplied compounds. In some embodiments, a disclosed compound is synthesized from a synthetically accessible or commercially available metal complex and one or more suitable binders.
[0190] In some embodiments, the present invention provides a method of preparing a compound of formula I, which comprises the reaction of the compound of formula V:
where: each of R1 and R2 is independently R, -OR, -SR, - N (R) 2, -OC (O) R, -SOR, -SO2R, - SO2N (R) 2, -C (O ) N (R) 2, - NRC (O) R or -NRSO2R; each R6 and R7 is halogen, -OR or a phosphorus-containing binder; each R is independently hydrogen or an optionally substituted group selected from C1-20 aliphatic, C120 heteroaliphatic having 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, phenyl, ferrocene, a 3-7 membered saturated or partially unsaturated carbocyclic ring , an 8-10 membered saturated, partially unsaturated or aryl bicyclic ring, a 5-6 membered heteroaryl monocyclic ring that has 14 heteroatoms independently selected from nitrogen, oxygen or sulfur, a 4-7 membered saturated or partially unsaturated heterocyclic ring which has 1-3 heteroatoms selected independently of nitrogen, oxygen or sulfur, a 7-10 membered saturated or partially unsaturated bicyclic heterocyclic ring which has 1-5 heteroatoms selected independently of nitrogen, oxygen or sulfur or an 8- bicyclic heteroaryl ring 10 members that have 1-5 heteroatoms selected independently of nitrogen, oxygen or sulfur, or: two or three R groups on the same nitrogen atom are taken together with nitrogen to form an optionally substituted 3-12 membered saturated, partially unsaturated or aryl ring that has 0-5 additional hetero atoms, not including the same nitrogen atom, selected independently of nitrogen, oxygen or sulfur; or: two R groups on the same oxygen atom are taken together with oxygen to form an optionally substituted saturated, partially unsaturated or 3-12 membered aryl ring that has 0-5 additional heteroatoms, not including the same oxygen atom, independently selected from nitrogen, oxygen or sulfur; n is 0, 1 or 2; each R8 is independently a monodentate ligand, or two R8 are taken together with their intervening atoms to form an optionally substituted bidentate group; and two or more of R1, R2, R6 R7 and R8 can be taken together with their intervening atoms to form an optionally substituted polyidentated ligand; with one or more suitable binders to form a compound of formula I:
wherein each of n, R1, R2, R3 R4 and R5 is independently as defined above or described herein.
[0191] In some embodiments, each of R6 R7 and R8 is independently selected from halogen and P (R ') 3, where each R' is independently as defined above or described herein. In some embodiments, each of R6 and R7 is independently halogen and each of R8 is independently P (R ') 3-. In some embodiments, n = 2, each of R6 and R7 is independently halogen, and each of R8 is independently P (R ') 3. In some modalities, n = 2, each of R6 and R7 is independently halogen, and each of R8 is independently P (R) 3.
[0192] In some embodiments, a compound of formula V is WO (CHR1R2) (P (R) 3) 2Cl2 or WO (CHR1R2) (P (R) 3) 2Br2, where each of R1 and R2 is independently as defined above or described herein, and each R is independently an optionally substituted group selected from C1-20 aliphatic or phenyl. In some embodiments, a compound of formula V is WO (CH-t-Bu) (PMe2Ph) 2Cl2. In some embodiments, a compound of formula V is WO (CH-t-Bu) (PMe3) 2Cl2.
[0193] In some embodiments, the present invention provides a simplified method for preparing oxo-tungsten-alkylidene complexes having the structure of formulas V, Va, and Vb. In some embodiments, a compound of formula V has the structure of formula Va:
where: each of R9 and R10 is independently halogen; and each of R1, R2, R8 and n is independently as defined above and described herein.
[0194] In some embodiments, the present invention provides a method of producing an oxo-tungsten-alkylidene complex, in which the alkylidene is prepared in tungsten. These methods differ from those in which the alkylidene group is "transferred" from another metal, for example, in the transformation below (L = PMe2Ph):

[0195] Exemplary methods in which the alkylidene group is prepared in tungsten are described here.
[0196] In some embodiments, the present invention provides a method of producing a compound of formula Va:
which comprises the use of a compound of formula VI:
wherein each of R1, R2, R5, R8, R9, R10 and n is independently as defined above and described herein. In some embodiments, the two R1 in formula VI are the same. In some embodiments, the two R2 in formula VI are the same. In some embodiments, the two R1 in formula VI are the same and the two R2 in formula VI are the same.
[0197] In some embodiments, a compound of formula VI has the structure of formula VI-a:
wherein each of R1, n, and R5 is independently as defined above and described herein. In some embodiments, the two R1 in formula VI-a are the same.
[0198] In some embodiments, each R1 in formula VI or VI-a is R. In some embodiments, each R1 in formula VI or VI-a is optionally substituted aliphatic C1-20. In some embodiments, each R1 in formula VI or VI-a is optionally substituted tert-butyl.
[0199] In some embodiments, each R5 in formula VI or VI-a is independently a monodentate ligand. In some embodiments, each R5 in formula VI or VI-a is independently a monodentate binder containing nitrogen. In some embodiments, each R5 in formula VI or VI-a is independently a monodentate linker that contains phosphorus.
[0200] In some embodiments, two R5s in formula VI-a are taken together with their intervening atoms to form an optionally substituted bidentate portion. In certain embodiments, two R5's are taken together to form an optionally substituted bidentate bipyridyl.
[0201] In some embodiments, a compound of formula VI is WO (CH2t-Bu) (beep) (beep = 2,2'-pyridine). In some embodiments, a compound of formula VI is WO (CH2CMe2Ph) (beep) (beep = 2,2'-pyridine).
[0202] In some embodiments, the method of preparing a compound of formula V or V-a above still comprises the use of a Lewis acid. In some embodiments, the method of preparing a compound of formula V or V-a above still comprises the use of a zinc salt. In some embodiments, the method of preparing a compound of formula V or V-a above further comprises the use of ZnCl2 (dioxane).
[0203] In some embodiments, the method of preparing a compound of formula V or V-a above further comprises the use of R3SiR9, wherein each of R and R9 is independently as defined above and described herein. In some embodiments, R3SiR9 is TMSCl.
[0204] In some embodiments, the method of preparing a compound of formula V or V-a above further comprises the use of R8, wherein R8 is as defined above and described herein. In some embodiments, R8 is PR3, where each R is independently as defined above and described herein. In some modalities, R8 is PMe2Ph.
[0205] In some embodiments, a method provided involves the formation of the alkylidene ligand in tungsten by abstraction of a hydrogen atom in the corresponding dialkyl precursor. In some embodiments, the alkylidene linker is = CH (t-Bu) and the two corresponding alkyl groups are -CH2t-Bu.
[0206] In some embodiments, the present invention provides a method of preparing a compound of formula Vb
: which comprises the reaction of a first compound of formula Va
with a second compound that has the structure of R11H or its salt, where: R11 is -OR; and each of R1, R2, R8, R9, R10, R and n is independently as defined above and described herein.
[0207] In some embodiments, a second compound in the above method is R11H. In some embodiments, a second compound in the above method is the R11H alkoxide or aryloxide salt. In some embodiments, a second compound is R11Li. In some embodiments, a compound of formula V-b is W (O) (CH-t-Bu) (OHMT) (PMe2Ph) Cl. In some embodiments, a compound of formula V-b is W (O) (CH-t-Bu) (OHIPT) (PMe2Ph) Cl. In some embodiments, a compound of formula V-b is W (O) (CH-t-Bu) (DFTO) (PMe2Ph) Cl.
[0208] In some embodiments, the present invention provides a method of preparing a compound that has the structure of formula VI:
which comprises the use of a compound that has the formula VII:
wherein each of R1, R2, R5, R9 and n is independently as defined above and described herein.
[0209] In some embodiments, a compound of formula VII is W (O) 2 (Cl) 2 (beep). In some embodiments, a compound of formula VII is W (O) 2 (Br) 2 (beep).
[0210] In some embodiments, the present invention provides a method of preparing a compound that has the structure of formula VI:
which comprises the reaction of a first compound that has the structure of formula VII
with a second compound comprising a portion
bonded directly to a metal, wherein each of R1, R2, R5, R9 and n is independently as defined above and described herein, and the two portions
in formula VI and the second compound are the same.
[0211] In some embodiments, the present invention provides a method of preparing a compound that has the structure of formula VI-a:
which comprises the reaction of a first compound that has the structure of formula VII
with a second compound comprising an Ip1 portion directly to a metal, wherein each of R1, R2, R5, R9 and n is independently as defined above and described herein, and the two R1 in formula VI-a and the second compound are equals.
[0212] In some embodiments, a second compound in the methods provided is a Grignard reagent. In supplied is a Grignard reagent that has the formula of R1CH (R2) MgR10. In some embodiments, a second compound in the methods provided is a Grignard reagent that has the formula of R1CH (R2) MgR10. In some embodiments, a second compound in the methods provided is a Grignard reagent that has the formula of R1CH2MgR10. In some embodiments, such a Grignard reagent is t-BuCH2MgCl. In some embodiments, such a Grignard reagent is PhC (Me) 2CH2MgCl.
[0213] In some embodiments, the present invention provides a method of preparing a compound that has the structure of formula VII:
which includes the use of W (R9) 6. In some modalities, such a method still includes the use of R5. In some embodiments, a method provided optionally further comprises the use of dimethoxyethane (DME). In some embodiments, a method provided still includes the use of TMS2O. In some embodiments, W (R9) 6 is WCl6.
[0214] In some embodiments, the present invention provides methods for preparing various types of oxo-alkylidene species from a compound of formula Vb including, without limitation, compounds having the structure of formula I. Exemplary compounds and methods are described below . provides a method of producing a compound of formula I, in which R3 is -OR and R4 is -N (R) 2, which comprises the reaction of a first compound of formula Vb, in which R11 is -R3, with a second compound of formula R2 H or its anionic amide salt; where each variable is independently as defined above and described here.
[0215] In some embodiments, the present invention provides a method of producing a compound of formula I, in which R3 is -OR and R4 is -N (R) 2, which comprises the reaction of a first compound of formula Vb, in whereas R11 is -R3, with a second compound of formula R2 H or its anionic amide salt; where each variable is independently as defined above and described here.
[0216] In some embodiments, R3 and R11 in the above method are -OR, where R is optionally substituted phenyl. An optionally substituted phenyl is intensively described in the specification including, without limitation, the modalities for R3, R4 and R11. In some embodiments, - OR is -OHMT. In some modalities, -OR is OHIPT. In some modalities, -OR is DFTO.
[0217] In some embodiments, a second compound in the above method is the anionic amide salt of R2NH. In some embodiments, a second compound in the above method is LiNR2. Exemplary modalities of R or -NR2 are intensely and independently defined above and described herein including, without limitation, modalities for R3 and R4. In some embodiments, two R groups are taken together with nitrogen to form an optionally substituted 5-membered heteroaryl ring that has 0-3 additional nitrogen atoms, not including the N of - N (R) 2 atom. Such rings include optionally substituted pyrrol-1-yl, pyrazol-1-yl, imidazol-1-yl and triazol-1-yl. In some embodiments, these rings are unsubstituted pyrrol-1-yl, pyrazol-1-yl, imidazol-1-yl and triazol-1-yl. In some embodiments, a compound of formula V-b is W (O) (CH-t-Bu) (OHMT) (PMe2Ph) Cl. In some embodiments, a compound of formula V-b is W (O) (CH-t-Bu) (OHIPT) (PMe2Ph) Cl. In some embodiments, a compound of formula V-b is W (O) (CH-t-Bu) (DFTO) (PMe2Ph) Cl. In some embodiments, a second compound is LiPh2Pir. In some embodiments, a second compound is LiMe2Pir. In some embodiments, a compound of formula I is W (O) (CH-t-Bu) (Ph2Pir) (OHMT). In some embodiments, a compound of formula I is W (O) (CH-t-Bu) (Ph2Pir) (OHIPT). In some embodiments, a compound of formula I is W (O) (CH-t-Bu) (Ph2Pir) (DFTO). In some embodiments, a compound of formula I is W (O) (CH-t-Bu) (Me2Pir) (OHMT) (PMe2Ph). In some embodiments, a compound of formula I is W (O) (CH-t-Bu) (Me2Pir) (OHIPT). In some embodiments, a compound of formula I is W (O) (CH-t-Bu) (Me2Pir) (DFTO).
[0218] As used here, Ph2Pir is
L ^ —and 2Pir is

[0219] In some embodiments, a second compound is LiN (C6F5) 2, and a compound of formula I is W (O) (CH-t-Bu) [N (C6F5) 2] (OHMT) (PPhMe2).
[0220] In some embodiments, the present invention provides a method of producing a compound of formula I, wherein each of R3 and R4 is independently -OR, which comprises: the reaction of a first compound of formula Vb, wherein R11 is R4 in formula I, with a second compound of formula R3H or its salt, where R3 is the same as R3 of formula I, where each variable is independently as defined above and described herein. provides a method of producing a compound of formula I, wherein R3 and R4 are equal and are -OR, which comprises: reacting a first compound of formula V-a with a second compound of formula R3H or its salt; where each variable is independently as defined above and described here.
[0221] In some embodiments, the present invention provides a method of producing a compound of formula I, in which R3 and R4 are equal and are -OR, which comprises: the reaction of a first compound of formula Va with a second compound of formula R3H or its salt; where each variable is independently as defined above and described here.
[0222] In some embodiments, a second compound is the R3H salt. In some embodiments, a second compound is R3Li. -OR exemplary for R3, R4 and R11 is intensely described above. In some embodiments, R is optionally substituted phenyl. In some modalities, R3 and R4 are the same. In some modalities, R3 and R4 are different. In some embodiments, one of R3 and R4 is -OHMT. In some modalities, one of R3 and R4 is -OHIPT. In some modalities, one of R3 and R4 is -DFTO. In some embodiments, both R3 and R4 are -OHMT. In some modalities, both R3 and R4 are -OHIPT. In some modalities, both R3 and R4 are -DFTO. In some embodiments, a compound of formula I is W (O) (CH-t-Bu) (OHMT) 2. In some embodiments, a compound of formula I is W (O) (CH-t-Bu) (OHIPT) 2. In some embodiments, a compound of formula I is W (O) (CH-t-Bu) (DFTO) 2. In some embodiments, at least one of R3 and R4 is not -O-2,6-Ph2C6H3.
[0223] In some embodiments, R3Li is LiOHMT. In some modalities, R3Li is LiOHIPT. In some embodiments, R3Li is LiODFT.
[0224] In some embodiments, the present invention provides a method of producing a compound of formula VIII-a
: which comprises the reaction of a first compound of formula Vb:
with a second compound of formula R11 H or its salt, where each variable is independently as defined above and described herein.
[0225] In some embodiments, a second compound is the R11H salt. In some embodiments, a second compound is R11Li. -Or exemplary OR for R11 and R11 is intensively described here above. In some embodiments, R is optionally substituted phenyl. In some modalities, R11 and R11 are the same. In some modalities, R11 and R11 are different. In some embodiments, one of R11 and R11 is -OHMT. In some modalities, one of Rn and Rn is -OHIPT. In some modalities, one of R11 and R11 is -DFTO. In some embodiments, both R11 and R11 are -OHMT. In some modalities, both R11 and R11 are -OHIPT. In some modalities, both R11 and R11 are -DFTO. In some embodiments, a compound of formula I is W (O) (CH-t-Bu) (OHMT) 2. In some embodiments, a compound of formula I is W (O) (CH-t-Bu) (OHIPT) 2. In some embodiments, a compound of formula I is W (O) (CH-t-Bu) (DFTO) 2. In some embodiments, at least one of R11 and R11 'is not -O-2,6- Ph2C6H3.
[0226] In some embodiments, R11 Li is LiOHMT. In some modalities, R11Li is LiOHIPT. In some embodiments, R11Li is LiODFT.
[0227] In some embodiments, the present invention provides a method of producing a compound of formula VIII-b,
which comprises the reaction of a first compound of formula Vb
with a second compound of formula R12H or its salt; wherein R12 is -OSiR3, and each of R1, R2, R8, R11, R and n is independently as defined above and described herein.
[0228] In some embodiments, a second compound is an R12H salt. In some embodiments, a second compound is R12Na. In some embodiments, a second compound is NaOSi (t-Bu) 3.
[0229] As described above, in some embodiments, neutral ligands, for example, neutral ligands containing nitrogen, oxygen and / or phosphorus for R5 and R8 (for example, bipyr and phosphine ligands), may be partially associated with W. In some modalities, this association can be detected by MRI. In some modalities, although not attached to a theory, the dissociation is caused by the greater steric demand for ligands other than neutral ligands. In some embodiments, a compound is detected or isolated without the neutral ligand, for example, without R5 or R8 (n = 0). In some embodiments, such a compound comprises OHIPT. In other embodiments, a compound is detected or isolated with one or more neutral linkers, for example, with R5 and / or R8 (n = 1 or n = 2). In some embodiments, such a compound comprises OHMT. In some embodiments, such a compound comprises OHIPT. In some embodiments, such a compound comprises DFTO. The present invention recognizes that, in the methods provided, neutral ligands (for example, R5 or R8) can dissociate as a result of the association of new ligands. A non-limiting example is when W (O) (CH-t-Bu) (OHMT) 2 is formed by reacting W (O) (CH-t-Bu) (OHMT) (PMe2Ph) Cl with LiOHMT.
[0230] In some embodiments, the present invention provides a method of producing a compound of formula IX:
which comprises the reaction of a first compound of formula Ic:
with a second compound comprising a double bond, wherein each variable is independently as defined above and described herein.
[0231] In some modalities, each of R3 and R4 is independently -OR. In some embodiments, R3 is -OSiR3 and R4 is independently -OR.
[0232] In some embodiments, a second compound comprising a double bond in the above method is a terminal olefin. In some embodiments, a second compound comprising a double bond is ethylene.
[0233] In some embodiments, the methods provided would be beneficial for the preparation and application of oxo-alkylidene compounds. For example, among other benefits, the methods provided use cheaper and widely available starting materials (eg WCl6), and / or simpler reaction and / or purification procedures. In some embodiments, the methods provided also produce compost with greater purity and / or activity.
[0234] In some embodiments, a binder is provided in a molar ratio of about 10: 1, 9: 1, 8: 1, 7: 1, 6: 1, 5: 1, 4: 1, 3: 1, 2: 1 or 1: 1 in relation to the metal complex. In some embodiments, a binder is provided in a molar ratio of about 0.9: 1, 0.8: 1, 0.7: 1, 0.6: 1, 0.5: 1, 0.4: 1 , 0.3: 1, 0.2: 1 or 0.1: 1 with respect to the metal complex. In certain embodiments, a binder is provided in a molar ratio of about 1: 1 to the metal complex. Those skilled in the art will note that the optimum molar ratio of binder to metal complex will depend, among other factors, on whether the binder is mono- or polyidentate.
[0235] In some embodiments, a binder is provided in a molar ratio of about 10: 1, 9: 1, 8: 1, 7: 1, 6: 1, 5: 1, 4: 1, 3: 1, 2: 1 or 1: 1 in relation to the metallic complex of formula III. In some embodiments, a binder is provided in a molar ratio of about 0.9: 1, 0.8: 1, 0.7: 1, 0.6: 1, 0.5: 1, 0.4: 1 , 0.3: 1, 0.2: 1 or 0.1: 1 with respect to the metallic complex of formula III. In certain embodiments, a binder is provided in a molar ratio of about 1: 1 to the metallic complex of formula III. Those skilled in the art will note that the optimum molar ratio of binder to metal complex will depend, among other factors, on whether the binder is mono- or polyidentate.
[0236] Conditions suitable for carrying out the methods provided generally employ one or more solvents. In certain embodiments, one or more organic solvents are used. Examples of such organic solvents include, without limitation, hydrocarbons such as benzene, toluene and pentane, halogenated hydrocarbons such as dichloromethane, or polar aprotic solvents, for example, ethereal solvents including ether, tetrahydrofuran (THF) or dioxanes , or mixtures of these. In certain embodiments, one or more solvents are deuterated.
[0237] In some embodiments, a single solvent is used. In certain embodiments, the solvent is benzene. In certain embodiments, the solvent is ether.
[0238] In some embodiments, mixtures of two or more solvents are used and, in some cases, may be preferred over a single solvent. In certain embodiments, the solvent mixture is a mixture of an ethereal solvent and a hydrocarbon. Exemplary mixtures of this type include, for example, an ether / benzene mixture. Solvent mixtures can be made up of equal volumes of each solvent or can contain one solvent in excess of the other solvent or solvents. In certain embodiments in which a solvent mixture is composed of two solvents, the solvents may be present in a ratio of about 20: 1, about 10: 1, about 9: 1, about 8: 1, about 7: 1, about 6: 1, about 5: 1, about 4: 1, about 3: 1, about 2: 1 or about 1: 1. In certain embodiments in which a solvent mixture comprises an ethereal solvent and a hydrocarbon, the solvents may be present in a ratio of about 20: 1, about 10: 1, about 9: 1, about 8: 1, about 7: 1, about 6: 1, about 5: 1, about 4: 1, about 3: 1, about 2: 1 or about 1: 1 hydrocarbon / ether solvent. In certain embodiments, the solvent mixture comprises a mixture of ether and benzene in a ratio of about 5: 1. Those skilled in the art would note that other mixtures and / or solvent ratios are contemplated here, that the selection of these other mixtures and / or solvent ratios will depend on the solubility of the species present in the reaction (for example, substrates, additives, etc.), and that the experimentation necessary to optimize the mixture and / or proportion of solvents would be routine in the art and not unnecessary.
[0239] Conditions suitable for the formation of a precursor complex or a compound supplied typically employ ambient reaction temperatures. In some embodiments, a suitable reaction temperature is about 15 ° C, about 20 ° C, about 25 ° C or about 30 ° C. In some embodiments, a suitable reaction temperature is about 15 ° C to about 25 ° C. In certain embodiments, a suitable reaction temperature is about 20 ° C, 21 ° C, 22 ° C, 23 ° C, 24 ° C or 25 ° C.
[0240] In certain embodiments, a method provided for preparing a precursor complex or a compound provided is carried out at an elevated temperature. In some embodiments, a suitable reaction temperature is about 25 ° C to about 110 ° C. In certain embodiments, a suitable reaction temperature is about 40 ° C to about 100 ° C, about 50 ° C to about 100 ° C, about 60 ° C to about 100 ° C, from about 70 ° C to about 100 ° C, about 80 ° C to about 100 ° C, or about 90 ° C to about 100 ° C.
[0241] In certain embodiments, a method provided for preparing a precursor complex or a compound provided is carried out at a temperature lower than room temperatures. In some embodiments, a suitable reaction temperature is about -100 ° C to about 10 ° C. In certain embodiments, a suitable reaction temperature is about -80 ° C to about 0 ° C, about -70 ° C to about 0 ° C, about -60 ° C to about 0 ° From about -50 ° C to about 0 ° C, from about -40 ° C to about 0 ° C, or from about -30 ° C to about 0 ° C.
[0242] In some embodiments, a method provided is carried out at different temperatures. In some embodiments, the reaction temperature changes in a method provided. In some embodiments, a method provided involves increasing the temperature from a lower temperature to a higher temperature. In some embodiments, a method provided comprises a temperature rise of about -80 ° C, about -70 ° C, about -60 ° C, about - 50 ° C, about -40 ° C, about - 30 ° C, about -20 ° C, about -10 ° C, and about 0 ° C to about 0 ° C, about 10 ° C, about 20 ° C, room temperature, about 22 ° C, about 25 ° C, about 30 ° C, about 40 ° C, about 50 ° C, about 60 ° C, about 70 ° C, about 80 ° C, about 90 ° C , about 100 ° C and about 110 ° C. In some embodiments, a method provided comprises an increase in temperature from about -30 ° C to 22 ° C. In some embodiments, a method provided comprises lowering the temperature from a higher temperature to a lower temperature. In some embodiments, a method provided comprises a temperature rise of about 110 ° C, about 100 ° C, about 90 ° C, about 80 ° C, about 70 ° C, about 60 ° C, about 50 ° C, about 40 ° C, about 30 ° C, about 25 ° C, about 22 ° C, room temperature, about 20 ° C, about 10 ° C, and about 0 ° C to about 0 ° C, about -10 ° C, about - 20 ° C, about -30 ° C, about -40 ° C, about -50 ° C, about -60 ° C, about -70 ° C, about -80 ° C, about -90 ° C and about -100 ° C.
[0243] Suitable conditions for the formation of a precursor complex or a compound supplied typically involve reaction times of about 1 minute to about 1 day. In some embodiments, the reaction time changes from about 0.5 hour to about 20 hours. In some embodiments, the reaction time changes from about 0.5 hour to about 15 hours. In some embodiments, the reaction time changes from about 1.0 hour to about 12 hours. In some modalities, the reaction time changes from about 1 hour to about 10 hours. In some modalities, the reaction time changes from about 1 hour to about 8 hours. In some modalities, the reaction time changes from about 1 hour to about 6 hours. In some embodiments, the reaction time changes from about 1 hour to about 4 hours. In some embodiments, the reaction time changes from about 1 hour to about 2 hours. In some modalities, the reaction time changes from about 2 hours to about 8 hours. In some modalities, the reaction time changes from about 2 hours to about 4 hours. In some embodiments, the reaction time changes from about 2 hours to about 3 hours. In certain embodiments, the reaction time is about 1 hour. In certain embodiments, the reaction time is about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 hours. In some embodiments, the reaction time is about 12 hours. In certain embodiments, the reaction time is less than about 1 hour. In certain embodiments, the reaction time is about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50 or 55 minutes. In some embodiments, the reaction time is about 30 minutes. EXAMPLE USES OF COMPOUNDS PROVIDED
[0244] As described herein, the compounds of formula I provided are particularly useful for metathesis reactions.
[0245] In some embodiments, the methods of using compounds provided involve the reaction of a first species and a second species to form a product comprising a double bond, wherein the double bond comprises an atom of the first species and an atom of the second species. In some embodiments, the first species and the second species are different. In some embodiments, the first species and the second species are the same. In some embodiments, the double bond may comprise a carbon atom of the first species and a carbon atom of the second species. The produced double bond can have a Z (for example, cis) or E (for example, trans) configuration. Those skilled in the art will understand the meanings of the terms "cis" or "Z" and "trans" or "E", as used within the context of the invention.
[0246] Some modalities may provide the ability to selectively synthesize, through a metathesis reaction, products that have a Z or E configuration around a double bond. In some embodiments, methods of using compounds of formula I of the present invention may provide the ability to synthesize compounds that comprise a disubstituted Z-olefin. In some embodiments, these methods are useful when applied to a wide range of olefin substrates, including those that have sterically small or large groups adjacent to the olefin. In some embodiments, the substrate olefins are terminal olefins. In some embodiments, the complexes of the present invention are useful in methods for the synthesis of Z-disubstituted enol ethers. In some embodiments, the complexes of the present invention are useful in methods for the synthesis of Z-disubstituted allyl amines. In some embodiments, the complexes of the present invention are useful in methods for the synthesis of Z-disubstituted allyl amides.
[0247] In some embodiments, a compound of formula I promotes selective Z-olefin metathesis reactions. In some embodiments, a compound of formula I promotes E-selective olefin metathesis reactions.
[0248] In some embodiments, a metathesis reaction using a compound of formula I produces a double bond in a Z: E ratio greater than about 1: 1, greater than about 2: 1, greater than about 3: 1, greater than about 4: 1, greater than about 5: 1, greater than about 6: 1, greater than about 7: 1, greater than about 8: 1, greater than about 9: 1, greater than about 95: 5, greater than about 96: 4, greater than about 97: 3, greater than about 98: 2 or, in some cases, greater than about 99: 1, as determined using the methods described herein (for example, HPLC). In some cases, about 100% of the double bond produced in the metathesis reaction can have a Z configuration. The selectivity for Z or cis can also be expressed as a percentage of product formed. In some cases, the product may be more than about 50% Z, more than about 60% Z, more than about 70% Z, more than about 80% Z, more than about 90 % Z, more than about 95% Z, more than about 96% Z, more than about 97% Z, more than about 98% Z, more than about 99% Z, or some cases, more than about 99.5% Z.
[0249] In some embodiments, a metathesis reaction using a compound of formula I produces a double bond in an E: Z ratio greater than about 1: 1, greater than about 2: 1, greater than about 3: 1, greater than about 4: 1, greater than about 5: 1, greater than about 6: 1, greater than about 7: 1, greater than about 8: 1, greater than about 9: 1, greater than about 95: 5, greater than about 96: 4, greater than about 97: 3, greater than about 98: 2 or, in some cases, greater than about 99: 1, as determined using the methods described herein (for example, HPLC). In some cases, about 100% of the double bond produced in the metathesis reaction can have an E configuration. The selectivity for E or trans can also be expressed as a percentage of product formed. In some cases, the product may be more than about 50% E, more than about 60% E, more than about 70% E, more than about 80% E, more than about 90 % E, more than about 95% E, more than about 96% E, more than about 97% E, more than about 98% E, more than about 99% E or, in some cases, more than about 99.5% E.
[0250] Without being bound by a particular theory, it is believed that Z-selectivity is caused, at least in part, by the small size of the oxo ligand in relation to R3, where R3 is as defined above and described here.
[0251] In some embodiments, a compound of formula I isomerizes a product. In some embodiments, a compound of formula I isomerizes a product Z. In some embodiments, a compound of formula I isomerizes a product Z slower than the formation of the product. In some embodiments, a compound of formula I isomerizes an E product. In some embodiments, a compound of formula I isomerizes an E product slower than product formation.
[0252] In some embodiments, a compound of formula I does not isomerize a product. In some embodiments, a compound of formula I does not isomerize a product Z. In some embodiments, a compound of formula I does not isomerize an product E.
[0253] In some embodiments, a compound of formula I, or the active catalyst formed by a compound of formula I, is stable under metathesis. In some embodiments, a compound of formula I, or the active catalyst formed by a compound of formula I, decomposes under metathesis. In some embodiments, a compound of formula I, or the active catalyst formed by a compound of formula I, decomposes under condition of metathesis within about 1 hour. In some embodiments, a compound of formula I, or the active catalyst formed by a compound of formula I, decomposes under metathesis within about 2 hours. In some embodiments, a compound of formula I, or the active catalyst formed by a compound of formula I, decomposes under metathesis within about 6 hours. In some embodiments, a compound of formula I, or the active catalyst formed by a compound of formula I, decomposes under metathesis within about 12 hours. In some embodiments, a compound of formula I, or the active catalyst formed by a compound of formula I, decomposes under metathesis within about 24 hours. In some embodiments, a compound of formula I, or the active catalyst formed by a compound of formula I, decomposes under metathesis within about 48 hours. In some embodiments, a compound of formula I, or the active catalyst formed by a compound of formula I, decomposes under metathesis within about 96 hours.
[0254] In some embodiments, a compound of formula I, or the active catalyst formed by a compound of formula I, decomposes before the isomerization of a product. In some embodiments, a compound of formula I, or the active catalyst formed by a compound of formula I, partially decomposes before the isomerization of a product. In some embodiments, a compound of formula I, or the active catalyst formed by a compound of formula I, decomposes before the isomerization of a product Z. In some embodiments, a compound of formula I, or the active catalyst formed by a compound of formula I, partially decomposes before the isomerization of a product Z. In some embodiments, a compound of formula I, or the active catalyst formed by a compound of formula I, decomposes before the isomerization of a product E. In some embodiments , a compound of formula I, or the active catalyst formed by a compound of formula I, partially decomposes before the isomerization of a product E.
[0255] In some embodiments, a metathesis reaction using a compound of the present invention produces a polymer in which the polymer is> 50% cis,> 50% syndiotactic. In some embodiments, a metathesis reaction using a compound of the present invention produces a polymer in which the polymer is> 60% cis,> 60% syndiotactic. In some embodiments, a metathesis reaction using a compound of the present invention produces a polymer in which the polymer is> 70% cis,> 70% syndiotactic. In some embodiments, a metathesis reaction using a compound of the present invention produces a polymer in which the polymer is> 80% cis,> 80% syndiotactic. In some embodiments, a metathesis reaction using a compound of the present invention produces a polymer in which the polymer is> 90% cis, 90% syndiotactic. In some embodiments, a metathesis reaction using a compound of the present invention produces a polymer in which the polymer is> 95% cis, 90% syndiotactic. In some embodiments, a metathesis reaction using a compound of the present invention produces a polymer in which the polymer is> 99% cis, 90% syndiotactic. In some embodiments, a metathesis reaction using a compound of the present invention produces a polymer in which the polymer is> 90% cis,> 90% syndiotactic. In some embodiments, a metathesis reaction using a compound of the present invention produces a polymer in which the polymer is> 95% cis,> 90% syndiotactic. In some embodiments, a metathesis reaction using a compound of the present invention produces a polymer in which the polymer is> 99% cis,> 90% syndiotactic. In some embodiments, a metathesis reaction using a compound of the present invention produces a polymer in which the polymer is> 99% cis,> 95% syndiotactic. In some embodiments, a metathesis reaction using a compound of the present invention produces a polymer in which the polymer is> 99% cis,> 97% syndiotactic.
[0256] In some embodiments, a metathesis reaction using a compound of formula I is further accelerated by the addition of a Lewis acid. In some embodiments, such a Lewis acid is B (C6F5) 3.
[0257] As mentioned above, compounds provided are useful for metathesis reactions. Exemplary methods and reactions of this type are described below.
[0258] It will be noted that, in certain modalities, each variable mentioned for the method above is as defined above and described in modalities presented here, alone and in combination. EXEMPLIFICATION
[0259] General comments. All manipulations were carried out in a dry box filled with nitrogen or in an air-free double collector Schlenk line. The solvents were sparged with nitrogen, passed through activated alumina and stored over 4  activated Linde molecular sieves. Methylene chloride-d2, chloroform-d3 and benzene-d6 were distilled from calcium hydride (CD2Cl2, CDCl3) or sodium cetyl (C6D6), and stored on 4 µ Linde molecular sieves. MRI spectra were recorded using Varian spectrometers at 500 (1H), 125 (13C), 121 (31P), 471 (19F) and 161 (11B) MHz, reported in δ (parts per million) in relation to tetramethylsilane (1H , 13C), 85% phosphoric acid (31P), CFCl3 (19F) or BF3-Et2O (11B), and referenced to the residual signals of 1H / 13C of the deuterated solvent (1H (δ): 7.16 benzene; methylene chloride 5.32, chloroform 7.26; 13C (δ): benzene 128.06; methylene chloride 53.84, chloroform 77.16), or 85% external phosphoric acid standards (31P (δ): 0.0) , C6F6 (19F (δ): - 169.4) and BF3-Et2O (11B (δ): 0.0). Midwest Microlab, Indianapolis, Indiana provided the results of the element analysis.
[0260] WO (CH-t-Bu) Cl2 (PMe2Ph) 2 (Wengrovius, J. FL; Schrock, RR Organometallics 1982, 1, 148-155), Li (Me2Pir) (Jiang, AJ; Simpson, J. FL ; Muller, P .; Schrock, RRJ Am. Chem. Soc. 2009, 131, 7.770-7.780), HIPTOH (Stanciu, C; Olmstead, MM; Phillips, AD; Stender, M .; Power, PP Eur. J. Inorg. Chem. 2003, 2003, 3,495-3,500), HIPTOLiN (Stanciu, C; Olmstead, MM; Phillips, AD; Stender, M .; Power, PP Eur. J. Inorg. Chem. 2003, 2003, 3,495-3,500 ), HMTOH (Dickie, DA; Macintosh, IS; Ino, DD; He, Q .; Labeodan, OA; Jennings, MC; Schatte, G .; Walsby, CJ; Clyburne, JAC Can. J. Chem. 2008, 86 , 20-31), HMTOLiN (Dickie, DA; Macintosh, IS; Ino, DD; He, Q .; Labeodan, OA; Jennings, MC; Schatte, G .; Walsby, CJ; Clyburne, JAC Can. J. Chem 2008, 86, 20-31), DCMNBD (Tabor, DC; White, F .; Collier, LW; Evans, SAJ Org. Chem. 1983, 48, 1.638-1.643) were prepared according to reported procedures. The substrates for olefin homo coupling reactions were distilled by CaH2 and stored in a glove box over molecular sieves. All other reagents were used as received, unless otherwise noted. Details of the distribution of the X-ray crystal structure.
[0261] Low temperature diffraction data ($ and a scans) were collected on a Bruker-AXS X8 Kappa Duo diffractometer coupled to a Smart APEX 2 CCD detector with Mo Ka radiation (À = 0.71073 Â) from a IμS. Absorption corrections and other corrections were applied using SADABS (Sheldrick, G.M. SADABS, v. 2.10 - “A Program for Area Dabsorption Corrections”; Broker AXS: Madison, WI, 2003). All structures were solved by direct methods of using SHELXS (Sheldrick, GM Acta Cryst. 1990, A46, 467-473) and refined against F2 in all data by minimum squares of total matrix with SHELXL-97 (Sheldrick, GM Acta Cryst. 2008, A64, 112-122) using established refinement approaches (Muller, P. Crystallography Reviews 2009, 15, 57-83). All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were included in the models in geometrically calculated and refined positions using a mooring model, except for alkylidene protons. The coordinates for the alkylidene hydrogen atoms were taken from the Fourier difference synthesis and the hydrogen atoms were subsequently refined semi-freely with the help of the distance constraint, unless observed differently. The isotropic displacement parameters of all hydrogen atoms were fixed at 1.2 times the Ueq value of the atoms to which they are attached (1.5 times for methyl groups). All altered atoms were refined with the help of similarity restrictions at distances of 1.2 and 1.3 and displacement parameters, as well as rigid binding restrictions for anisotropic displacement parameters.
[0262] The compound W (O) (CH-t-Bu) (OHIPT) Cl (PMe2Ph) (I-1) crystallizes in the monoclinic space group P21 / c with a molecule in the asymmetric unit. The tungsten atom, chloride, oxo and alkylidene ligands were modeled as a two-component disorder and the proportion of occupations refined to 0.9130 (18). It was found that one of the iPr groups was also altered over two positions, the proportion of occupations refined to 0.694 (17). The anisotropic displacement parameters for chloride (C11, C11A), oxo (O2, O2A) and a carbon (C1, C1A) in the alkylidene have been restricted to be equivalent, in pairs. The coordinates for the hydrogen atom attached to C1 were taken from the Fourier difference synthesis as noted above. However, the hydrogen atom attached to C1A, the minor component of the disturbance, cannot be found in the Fourier difference synthesis and was included in the model in a geometrically calculated and refined position using a mooring model.
[0263] The compound W (O) (OHIPT) (Me2Pir) (I-2) crystallizes in the monoclinic space group P21 / n with a molecule in the asymmetric unit. One of the aryl groups in the alkoxide ligand was modeled as a two-component disorder and the proportion of the two-component occupations was refined to 0.637 (5). The anisotropic displacement parameters of all atoms in this disorder were restricted to be equivalent, in pairs. The higher residual electron density was modeled as a second tungsten position and the relative occupation of the two components refined to 0.9787 (4). The anisotropic displacement parameters of the two components were restricted to be equivalent. Oxo, pyrrolid and alkylidene were observed in the Fourier difference synthesis, but the refinement of these ligands as a disorder was unstable and, therefore, an alternative site was modeled only for tungsten.
[0264] The compound W (O) (CH-t-Bu) (OHMT) (Me2Pir) (PMe2Ph) (I-4) crystallizes in the triclinic space group P-1 with a molecule in the asymmetric unit together with a molecule and pentane sock. Half of a pentane molecule is located near a crystallographic inversion center and altered accordingly, which leads to a non-integer value for carbon.
[0265] The compound W (O) (B (C6F5) 3 (OHMT) (Me2Pir) (I-6) crystallizes in the monoclinic space group P21 / n with a molecule in the asymmetric unit.
[0266] We prepare W (O) (CH-t-Bu) (OHIPT) (Me2Pir) (where Me2Pyr = 2,5-dimethylpyrrolid) from W (O) (CH-t-Bu) (PMe2Ph) 2Cl2 as the starting material. The reaction between WO (CH-t-Bu) Cl2 (PMe2Ph) 2 and LiOHIPT in benzene at 22 ° C for 14 hours led to the isolation of WO (CH-t-Bu) Cl (OHIPT) (PMe2Ph) (I-1 ) whitish at 60% yield. Two isomers of I-1 are present in a 3: 2 ratio according to spectra of 1H, 13C and 31P RNM. Both are synkylidenes based on JCαH values for the 123 Hz (major isomer) and 117 Hz (minor isomer) alkylidene. Phosphine remains bound to tungsten on the MRI time scale (JPW = 420 Hz and 379 Hz, respectively) at 22 ° C. A crystal X-ray structure (Figure 1) revealed a square-pyramidal geometry distorted with the apical neopentilidene ligand and the trans phosphine ligand for chloride. Alkylidene was found to be altered under syn and anti orientations in a ratio of 91: 9. One possibility is that the other isomer has a similar structure in which the OHIPT and C1 ligands have exchanged positions.
Synthesis of WO (CH-t-Bu) (OHIPT) Cl (PMe2Ph) (I-1).
[0267] A solution of WO (CH-t-Bu) Cl2 (PMe2Ph) (300.0 mg, 0.486 mmol) in 10 ml of benzene was mixed with a solution of HIPTOLiN (247.1 mg, 0.489 mmol, 1, 01 equivalent) in 5 ml of benzene. The yellow, cloudy reaction mixture was stirred at room temperature for 14 h. The solvent was removed in vacuo to generate a yellow solid. The product was extracted into toluene (5 ml) and LiCl was removed by filtration through a bed of Celite. Toluene was removed in vacuo to generate a pale yellow crystalline solid. The product was triturated with pentane (5 ml) and the resulting suspension was filtered. The whitish solid was collected (280.2 mg, 60% yield). Two isomers in a ratio of 61:39 were formed according to MRI spectra; only non-overlapping alkylidene signals are listed: Main isomer 1H-RNM (C6D6) δ 9.36 (d, 1, WCH-t-Bu, 3JHP = 3 Hz, 2JHW = 11 Hz); 13C-RNM (C6D6) δ 292.4 (d, WCH-t-Bu, CH = 123 Hz, 2JCP = 12 Hz, 1JCW = 163 Hz); 31P-RNM (C6D6): δ 12.89 (s, w = 420 Hz). Minor isomer: 1H-RNM (C6D6): δ 8.89 (d, 1, WCH-t-Bu, 3JHP = 3 Hz, 2JHW = 13 Hz); 13C {1H} -RNM (C6D6): δ 278.7 (d, WCH-t-Bu, 1JCH = 117 Hz, 2JCP = 16 Hz, 1JCW = 188 Hz); 31P-RNM (C6D6): δ 16.15 (s, 1JPW = 379 Hz). Anal. calculated for C49H70ClO2PW: C, 62.52; H, 7.50. Found: C, 62.31; H, 7.49. Table 2. Crystal data and structure refinement details for W (O) (CH-t-Bu) (OHIPT) Cl (PMe2Ph) (I-1).


[0268] The reaction of I-1 with ethylene resulted in the formation of methylidene WO (CH2) (HYPTO) Cl (PMe2Ph) (I-10) complex, as confirmed by data from 1H-RNM in situ (two doublets of doublets) , δ = 8.64 and 10.44 ppm, 2JHH = 10 Hz, 3JHp = 4 Hz). The methylidene complex decomposes into solution in 24 hours.

[0269] Treatment of I-1 with Li (Me2Pir) in benzene at 60 ° C for 16 hours led to the formation of yellow W (O) (CH-t-Bu) (OHIPT) (Me2Pir) (I-2) in 80% isolated yield. An X-ray structure (Figure 2) showed that I2 has a pseudotetrahedral geometry, a syn alkylidene and a n1 ligand - Me2Pyr-
[0270] Synthesis of WO (CH-t-Bu) (Me2Pir) (HYPTO) (I-2). A portion of Li (Me2Pir) (56.4 mg, 0.558 mmol, 1.02 equivalent) was added as a solid to a solution of WO (CH-t-Bu) (HIPTO) Cl (PMe2Ph) (515.0 mg , 0.547 mmol) in 10 ml of benzene. The reaction mixture was transferred to a Schlenk type flask of solvent equipped with a Teflon valve, degassed and heated to 60 ° C for 16 h with rapid stirring. The color of the solution changed from pale yellow to bright yellow. The volatiles were removed by heating to 60 ° C in vacuo. The resulting yellow solid was triturated with 5 ml of benzene and LiCl was removed by filtration through a bed of Celite. Benzene was removed in vacuo leaving a bright yellow solid. The product was triturated with 5 ml of pentane and filtered. The filtrate was left in a refrigerator at -30 ° C for 1 day to generate a yellow crystalline solid. Two harvests were combined (378.2 mg, 80% yield): 1H-RNM (C6D6) δ 9.40 (s, 1, WCH-t-Bu, 2JHW = 10 Hz), 7.25 (m, 2 , Ar-H), 7.20 (m, 2, Ar-H), 7.12 (d, 2, Ar-H), 6.91 (t, 1, Ar-H), 5.99 (s , 2, Pir-H), 2.85 (overlapping septet, 6, CHMe2), 1.94 (s, 6, Pir-Me), 1.30 (d, 6, CHMe2), 1.29 (d, 6, CHMe2), 1.29 (d, 6, CHMe2), 1.21 (s, 9, WCH-t-Bu), 1.17 (superimposed d, 12, CHMe2), 1.10 (d, 6 , CHMe2); 13C {1H} -RNM (C6D6) δ 274.4 (WCH-t-Bu ,, 1JCH = 125 Hz, 1JCW = 155 Hz), 158.1, 149.1, 147.3, 146.9, 132, 9, 131.9, 131.1, 123.2, 121.9, 121.7, 110.8, 43.1, 33.9, 31.4, 31.3, 25.7, 24.5, 24.5, 24.4, 24.3, 18.4. Anal. calculated for C47H67NO2W: C, 65.50; H, 7.84; N, 1.63. Found: C, 65.30; H, 7.78; N, 1.60. Table 3. Crystal data and structure refinement data for WO (CH-t-Bu) (Me2Pir) (HIPTO) (I-2).


[0271] The analogous reaction between W (O) (CH-t-Bu) (PMe2Ph) 2Cl2 and LiOHMT (OHMT = O-2,6-dimesithylphenoxide) in benzene at 22 ° C for 3 h led to the isolation of WO ( CH-t-Bu) Cl (OHMT) (PMe2Ph) (I-3) whitened in 70% yield. As with I-1, the 1H-NMR spectrum of the product contains two alkylidene doublet resonances that correspond to two 87: 13 isomers of I-3. The values of 1JCH, 122 and 116 Hz, suggest that both isomers are syn alkylidenes. Synthesis of WO (CH-t-Bu) (HMTO) Cl (PMe2Ph) (I-3).
[0272] A solution of WO (CH-t-Bu) Cl2 (PMe2Ph) (1,000.0 mg, 1.620 mmol) in 15 ml of benzene was added to a portion of solid HMTOLiN (572.3 mg, 1.701 mmol, 1 , 05 equivalent). The yellow, cloudy reaction mixture was stirred at room temperature for 3 h. The solvent was removed in vacuo to generate a yellow solid. The product was extracted into toluene (10 ml) and LiCl was removed by filtration through a bed of Celite. Toluene was removed in vacuo to produce a yellow crystalline solid. The product was triturated with pentane (10 ml) and the resulting suspension was filtered. The yellow solid product was collected (872.0 mg, 1.128 mmol, 70% yield). Two isomers in a ratio of 87:13 were formed according to MRI spectra; only non-overlapping alkylidene signals are listed: Main isomer 1H-RNM (C6D6) δ 9.34 (d, 1, WCH-t-Bu, 3JHP = 3 Hz, 2JHW = 8 Hz); 13C- RNM (C6D6): δ 295.1 (d, WCH-t-Bu, 1JCH = 122 Hz, 2JCP = 11 Hz, 1JCW = 168 Hz); 31P-RNM (C6D6): δ 13.40 (s, 1JPW = 416 Hz). Minor isomer 1H-RNM (C6D6) δ 9.03 (d, 1, WCH-t-Bu, 3JHP = 3 Hz, 2JHW = 13 Hz); 13C {1H} -RNM (C6D6): δ 278.6 (d, WCH-t-Bu, 1JCH = 116 Hz, 2JCP = 15 Hz, 1JCW = 187 Hz); 31P-RNM (C6D6): δ 15.64 (s, 1JPW = 386 Hz). Anal. calculated for C37H46ClO2PW: C, 57.49; H, 6.00. Found: C, 57.52; H, 5.99.
[0273] In some embodiments, the synthesis of WO (CH-t-Bu) (HMTO) Cl (PMe2Ph) (I-3) can also be carried out by reaction of compound WO (CH-t-Bu) Cl2 (PMe2Ph) with an equivalent of HMTOLiN (HMTO = hexamethylterphenoxide) in toluene at room temperature to generate WO (CH-t-Bu) (HMTO) Cl (PMe2Ph). The 1H-NMR spectrum of the product contains two doublets of alkylidene proton that correspond to two isomers of I-3 in the ratio of 87:13. The values of 1JCH, 122 and 166 Hz, suggest that both species are syn alkylidenes.
[0274] The addition of Li (Me2Pir) to I-3 in toluene at - 30 ° C with subsequent stirring at 22 ° C for 10 hours led to W (O) (CH-t-Bu) (OHMT) (Me2Pir) (PMe2Ph) (I-4) yellow in 70% isolated yield. An X-ray structure from I-4 (Figure 3) showed that it is a square pyramid with the neopentilidene syn in the apical position and the trans-linked phosphine to the pyrrolidide. Synthesis of WO (CH-t-Bu) (Me2Pir) (HMTO) (PMe2Ph) (I-4).
[0275] A portion of Li (Me2Pir) (86.3 mg, 0.854 mmol, 1.1 equivalent) was added as a solid to a cold (-30 ° C) solution of WO (CH-t-Bu) (HMTO ) Cl (PMe2Ph) (600.0 mg, 0.776 mmol) in 15 ml of toluene. The reaction mixture was stirred at room temperature for 10 h. Toluene was removed in vacuo. The resulting brown oil was triturated with 5 ml of toluene and LiCl was removed by filtration through a bed of Celite. Toluene was removed in vacuo leaving a brown oil. The product was ground with 5 ml of pentane causing a pale yellow solid to precipitate. The product was filtered and washed with 5 ml of cold pentane. The filtrate was reduced in volume to approximately 3 ml and left in a refrigerator at - 30 ° C for 1 day generating yellow crystals. Two harvests were combined (452 mg, 70% yield): 1H-RNM (48 mM in C6D6) δ 9.14 (wide s, 1, WCH-t-Bu), 7.30 (m, 2, PMe2Ph) , 7.05 (m, 3, PMe2Ph), 7.00 (m, 2, Ar-H), 6.88 (m, 5, Ar-H), 6.10 (s, 2, Pir-H) , 2.20 (s, 6, Pir-Me), 2.08 (overlapping singlets, 18, Ar-Me), 1.11 (s, 6, PMe2Ph), 1.02 (s, 9, WCH-t -Bu); 13C {1H} -RNM (48 mM C6D6): δ 278.9 (broad, WCH-t-Bu), 158.5, 140.1, 137.6, 137.1, 136.7, 134.6, 131.9, 131.0, 130.9, 130.6, 129.3, 129.0, 128.6, 128.5, 128.4, 125.4, 125.2, 125.0, 122, 5, 109.9, 43.6, 32.6, 21.4, 21.2, 20.7, 17.5. 31P-RNM (48 mM C6D6): δ -25.5 (wide s); 1H-RNM (20 mM in CD2Cl2, -30 ° C) δ 9.92 (expanded s, 1, WCH-t-Bu), 7.48 (m, 2, PMe2Ph), 7.41 (m, 3, PMe2Ph), 6.94 (m, 7, Ar-H), 5.70 (s, 1, Pir-H), 5.66 (s, 1 Pir-H), 2.37 (s, 3, Ar - Me), 2.34 (s, 3, Ar-Me), 2.29 (s, 3, Ar-Me), 2.23 (s, 3, Ar-Me), 1.93 (s, 3 , Ar-Me), 1.88 (s, 3, Ar-Me), 1.62 (s, 3, Pir-Me), 1.54 (m, 6, PMe2Ph), 1.30 (s, 3 , Pir-Me), 0.52 (s, 9, WCH-t-Bu); 13C {1H} -RNM (20 mM in CD2Cl2, -30 ° C): δ 293.16 (WCH-t-Bu, CH = 125 Hz), 160.0, 139.3, 138.6, 136.7 (d), 135.0, 134.8, 134.3, 134.0, 133.5, 131.8, 131.6, 131.2, 130.6, 130.5 (d), 130.4 , 130.1, 129.4, 129.2, 128.6 (d), 128.2, 120.0, 107.3, 105.8, 44.0, 30.8, 21.9, 21, 6, 21.4, 21.0, 20.6, 18.7, 18.8, 13.9 (d), 11.0 (d). 31P-RNM (20 mM in CD2Cl2, -30 ° C): δ -1.80 (s, 1JPW = 289 Hz). Anal. calculated for C43H54NO2PW: C, 62.10; H, 6.54; N, 1.68. Found: C, 61.95; H, 6.73; N, 1.43. Table 4. Crystal data and structure refinement details for W (O) (OHMT) (CH-t-Bu) (Me2Pir) (PMe2Ph) (I-4).



[0276] The PMe2Ph ligand in I-4 is partially dissociated at room temperature and quickly exchanges the metal. The alkylidene resonance is wide and its chemical displacement is concentration-dependent (8.57-9.14 ppm for 4 mM - 48 mM solutions in C6D6). Studies of 1H- and 31P-RNM at variable temperature of a 20 mM solution of I-4 in CD2Cl2 showed that the phosphine is "turned on" below -30 ° C, as indicated by an acute signal of 31P that corresponds to the ligand coordinated (1.80 ppm, 1JPW = 289 Hz). Based on the chemical shift to free and coordinated phosphine, the equilibrium constant value for phosphine dissociation can be estimated as 0.015 M at room temperature. This value corresponds to 57% phosphine dissociation in a 20 mM solution of I-4 in C6D6.
[0277] Both I-2 and 1-4 react with ethylene to generate an unsubstituted metallacyclobutane (and t-butylethylene) complex that has a square pyramidal structure (presumably with the oxo ligand in the apical position) based on chemical displacements of metallacycle protons in the range of 0.7-4.5 ppm (Feldman J .; Schrock, RR Prog. Inorg. Chem. 1991, 39, 1). With I-2, the reaction with ethylene is relatively slow and we propose that an intermediate square pyramidal β-t-butylmethylcyclobutane complex can be observed before t-butylethylene is formed. In the case of compound I-4, a mixture of an unsubstituted square pyramidal metallocycle and methylidene is easily formed by adding ethylene. In both systems, metallacycles slowly decompose over a 24-hour period in unidentified products. A square pyramidal metallacyclobutane made of imidoalkylidenes has been proposed to move further away from the transition state to loss of olefin than is alternative metallocycle TBP (Feldman, J .; Davis, WM; Thomas, JK; Schrock, RR Organometallics 1990 , 9, 2,535).
[0278] Compound I-2 (0.01 M solution in C6D6) reacts with 1 ethylene atmosphere with a rapid color change of the solution from yellow to red. In 10 min. approximately 50% of the I-2 is converted into a square pyramidal metal cycle, as evidenced by the appearance of multiplets in the region of 4.6-1.8 ppm (Figure 6, lower) (Feldman, J .; Davis, WM; Thomas, JK; Schrock, RR Organometallics 1990, 9, 2,535). At the same time, no sign of 3,3-dimethyl-1-butene was observed. Therefore, it is proposed that the substituted metallocycle is formed in the initial stage of the reaction. The DEH-NMR spectrum recorded after 1 h (Figure 6, middle) showed almost complete disappearance of the metallocycle multiplets that were observed in the 10 min spectrum and formation of 3,3-dimethyl-1-butene and non-square pyramidal metalacyclobutane substituted. DCMNBD ROMP.
[0279] In a glove box filled with nitrogen, a solution of monomer (50.0 mg, 50 equivalents) in 1.0 ml of toluene was added to a solution of a catalyst in 0.2 ml of toluene. The mixture was stirred for 4 h. Aliquots were removed and diluted with CDCl3 to monitor the progress of the reaction. After completion of the reaction, 0.5 ml of benzaldehyde was added to the air and stirred for 30 min. The mixture was added dropwise to 50 ml of methanol with rapid stirring. A fine white solid formed immediately, and the mixture was stirred for 10 h. The polymer was removed by filtration on a glass frit and dried under vacuum.
[0280] Both I-2 and I-4 serve as initiators for the polymerization of 5,6-dicarbomethoxynorbornadiene (DCMNBD). Polymerization of 50 equivalents of DCMNBD is relatively slow with I-2 and propagation is faster than initiation. The resulting polymer is> 99% cis, 90% syndiotactic. Polymerization of 50 equivalents of DCMNBD with I-4 is relatively fast and the entire initiator is consumed. The resulting polymer is> 99% cis, 98% syndiotactic (Schrock, R.R .; Muller, P .; Hoveyda, A.H. J. Am. Chem. Soc. 2009, 131, 7,962).
[0281] Compound I-2 reacts with DCMNBD in toluene slowly to generate poly-DCMNBD> 99% cis, 90% syndiotactic. The polymerization of 50 equivalents of the monomer was complete in 90 min. Monitoring the progress of the in situ reaction on CD2Cl2 by 1H-MRI revealed that only 20% of the starting neopentylidene was consumed in 40 min.
[0282] Compound I-4 easily reacts with ethylene in benzene to form a metallocycle together with a methylidene complex in a 1: 1 ratio after 10 min. The metallocycle resonances are in the range of 0-4.5 ppm, which suggests a square-pyramidal geometry. In the case of I-4, however, 3,3-dimethylbutene formed rapidly, indicating that only unsubstituted tungstacyclobutane was present. Both the metallocycle and methylidene decomposed in up to 1 h in benzene. Terminal olefin homo coupling.
[0283] In a glove box filled with nitrogen, pure substrate (200 mg) was added to a solid catalyst in a 60 gram flask. The vial was placed in a 20 ml scintillation vial and sealed. The reaction mixture was stirred at 22 ° C and aliquots were collected. The aliquots were extinguished outside a box by exposure to air and addition of CDCl3. The conversion and selectivity of the reactions were monitored by 1H-MRI.
[0284] Homo coupling of pure terminal olefins with I-2 occurs slowly (hours) at room temperature. In contrast, I-4 was found to be highly active and highly Z-selective (Table 5). A catalyst load of just 0.2 mol% yielded up to 88% conversion in 6 h for several of the six chosen substrates. No trans products can be observed in 1H-NMR spectra of Z products. Table 5. Conversions into Z-selective metathesis homo-coupling products of I-4 terminal olefins. THE
a S1 = 1-octene, S2 = allylbenzene, S3 = pinacolate allylboronic acid ester, S4 = allyl-SiMe3, S5 = 1-decene, S6 = methyl-10-undecenoate. b The aliquot was collected after 7 h.
[0285] Clearly the formation of product Z is highly selective. Only a small increase in conversion was found for longer reaction times (> 6 h), which suggests that most of the catalyst decomposed at this stage. The decomposition of a catalyst before the isomerization of product Z into E may be a desirable feature of the coupling reaction. The reactions were performed on a 200 mg scale in a closed vessel with a volume of approximately 20 ml. The homo-coupling of 1-decene under vacuum of 0.5 Torr did not show a significant increase in turnover compared to the reaction performed under 1 nitrogen atmosphere. Without sticking to a particular theory, we related the relatively low turnover in the case of allyl-TMS (S4) to steric issues and, in the case of methyl-10-undecenoate (S6, with 1% catalyst load), to the bond from ester to W.
[0286] The results of homo coupling (HC) of 1-octene in 5-decene catalyzed by I-2 are shown in Table 6. The reaction rate is higher compared to the W (NAr) catalyst (C3H6) (3 , 5-Me2Pir) (HIPTO) recently reported analogue (32% conversion in 16 h, 4 mol% catalyst load) (Marinescu, SC; Schrock, RR; Muller, P .; Takase, MK; Hoveyda, AH Organometallics , 2011, 30, 1,780). It was found that the Z-selectivity was only 70-72% and declined as the reaction progressed. Table 6. Homo-coupling of 1-octene in the presence of I-2.

[0287] Compound I-4 has been found to be an excellent catalyst for ROMP and HC of terminal olefin reactions. For example, the polymerization of 50 equivalents of DCMNBD was complete in less than 10 min and the isolated polymer was all-cis and 98% syndiotactic. The results of homo-coupling of terminal olefins at room temperature with a 4 mol% catalyst load are listed in Table 7. The reactions are fast with high conversion being obtained within 3 h. The products are> 98% cis, that is, no trans products can be observed in 1H-RNM spectra. Little change in conversion was found after longer reaction times (> 10 h), which suggests that the catalyst decomposes over time. Without being attached to a particular theory, how isomerization of a Z product is believed to be the main reason for a decline in Z-selectivity with reaction time for tungsten imido-alkylidenes (Jiang, AJ; Zhao, Y .; Schrock, RR; Hoveyda, AHJ Am. Chem. Soc. 2009 131 16630), the decomposition of a catalyst before the point when this side reaction probably occurs may actually be desirable. Table 7. Homo coupling of terminal olefins to benzene in the presence of 4 mol% I-4.


[0288] Homo-coupling of pure 1-octene catalyzed by I-4 led to similarly high conversion and Z-selectivity for smaller catalyst loads (of only 0.2 mol%, see Table 8). For example, 72% conversion was obtained in 24 h. Table 8. Homo coupling of pure 1-octene in the presence of I-4.

[0289] The reactivity of I-2 in the reactions of both HC and ROMP in the presence of Lewis acids has been studied. It was found that the presence of B (C6H5) 3 or B (C6F5) 3 markedly increased the reaction rates. The results of homo-coupling of 1-octene in benzene solution, as well as in the pure substrate, are summarized in Tables 9 and 10. The addition of a strong Lewis acid equivalent B (C6F5) 3 dramatically increases the reactivity of oxo complex - tungsten-alkylidene (78% conversion in 15 min with 4 mol% catalyst load: compare with 15% conversion to I-2 in 2 h under similar conditions). Z- selectivity declined. At the same time, the addition of a milder Lewis acid equivalent B (C6H5) 3 led to increased reactivity, while the catalyst Z-selectivity was preserved. Table 9. Homo-coupling of 1-octene solution in benzene in the presence of I-2 with added Lewis acid.
Table 10. Homo coupling of pure 1-octene in the presence of I-2 with an equivalent of Lewis acid added.

[0290] I-2-catalyzed DCMNBD ROMP is significantly accelerated in the presence of Lewis acids. Polymerization of 50 equivalents of the monomer was found to be complete in less than 25 min with 40 equivalents of DCMNBD consumed in 10 min when an equivalent of B (C6F5) 3 was added to I-2. Under the same conditions, only six equivalents of the monomer reacted with I-2 without the presence of LA. The initiation reaction remains slow in the presence of B (C6F5) 3 (it was found that only 8-10% of the starting neopentilidene reacted with the monomer); however, the rate of spread increases dramatically. It is possible that a stronger Lewis acid adduct is formed with the insertion product than with the sterically packed neopentilidene initiator, thereby increasing the spread rate. Interestingly, the high activity of I-2 + B (C6F5) 3 was observed even in the presence of a large excess of monomer that has Lewis base sites, probably as a consequence of the higher alkalinity of oxo-tungsten-alkylidene.
[0291] Similar results were obtained when B (C6H5) 3 was used as an additive. In the first 10 min of the reaction, 10 equivalents of the monomer were consumed. It was found that 20-25% of I-2 reacted in 60 min.
[0292] The study by 1H-MRI at variable temperature (VT) of the mixture of I-2 and 0.5 equivalent of B (C6F5) 3 in CD2Cl2 showed that the formation of LA adduct can be observed at low temperatures (Figure 7). The alkylidene peak expands and changes downward with cooling from 22 ° C to -30 ° C. At -50 ° C, two peaks, a large one at 10.38 ppm and a more acute one at 8.86 ppm, are observed in the alkylidene region. The two alkylidene peaks become more acute at -80 ° C. This change is accompanied by the appearance of eight peaks in the aromatic pyrrolide region. The 1H-RNM of I-2 in CD2Cl2 at -80 ° C showed that the 8.86 ppm alkylidene signal, as well as two pyrrolide proton signals, belong to the LA-free MAP (Figure 7, lower). It is possible that the formation of the LA adduct could lead to stabilization of the n5 coordination mode of pyrrolide at low temperatures to compensate for the deficiency of electron density in the metal center.
[0293] The addition of Lewis acids to I-4 significantly accelerates metathesis reactions. For example, the addition of B (C6F5) 3 to I-4 resulted in a 90% conversion in 1 h for 1-octene homo-coupling with 0.2 mol% catalyst load. The homo-coupling metathesis reaction generates the thermodynamic mixture (20% of Z). Table 7 presents more data.
[0294] The addition of two equivalents of B (C6F5) 3 to I-4 led to the formation of (Me2PhP) (B (C6F5) 3) and I-6. Lewis acid at I-6 is labile at room temperature, as demonstrated by an extended alkylidene signal in the spectrum of 1H-NMR at 7.30 ppm. The 1H-RNM spectrum of 45 mM adduct solution at -60 ° C shows an acute alkylidene resonance at 7.06 ppm. An X-ray structure from I-6 showed that B (C6F5) 3 is coordinated with the oxo ligand (Figure 5). The W1-O2-B1 unit is curved (the angle of W1- O2-B1 is 159.9 (1) °). The distance W1-O2 is elongated (1,759 (2) Â) from that in I-4 (1,717 (2) Â) or I2 (1,695 (3) Â) and is slightly shorter than in B ( C6F5) 3 of reported oxo-tungsten complexes (Barrado, G .; Doerrer, L .; Green, ML FL; Leech, MAJ Chem. Soc., Dalton Trans. 1999, 1.061; Galsworthy, JR; Green, JC; Green , ML FL; Muller, MJ Chem. Soc., Dalton Trans. 1998, 15; Wolff, F .; Choukroun, R .; Lorber, C; Donnadieu, B. Eur. J. Inorg. Chem. 2003, 628; Sanchez Nieves, J .; Royo, P .; Mosquera, MEG Eur. J. Inorg. Chem. 2006, 127). A relatively weak coordination of B (C6F5) 3 for oxo is also indicated by the strength of the B1-O2 bond (1,571 (3) A), which is longer than in any B (C6F5) 3 adducts of metal complexes transition-oxo (1,484 (3) -1,558 (2) A) in the literature. The mean values of the angles of C-B-C and O-B-C (112.6 ° and 106.1 °, respectively) also suggest that B (C6F5) 3 is relatively weakly coordinated with oxo. Synthesis of W (O) (B (C6F5) 3) (CH-t-Bu) (OHMT) (Me2Pir) (I-6).
[0295] An ice-cold (-30 ° C) suspension of B (C6F5) 3 (37.3 mg, 0.073 mmol, 2.02 equivalents) in 2 ml of pentane was added to an ice-cold suspension (-30 ° C) of WO (CH-t-Bu) (Me2Pir) (HMTO) (PMe2Ph) (30.0 mg, 0.036 mmol) in 5 ml of pentane with rapid stirring. The color of the mixture changed from yellow to orange and a white precipitate gradually formed. The volume of solvent was reduced to approximately 3 ml and the mixture was filtered. The volume of the orange filtrate was reduced to approximately 1 ml and the solution was placed in the freezer at -30 ° C. Within three days, orange crystals formed. The MRI signals are listed for a 45 mM solution of I-4: B (C6F5) 3 in CD2Cl2 at - 60 ° C, generated in situ from WO (CH-t-Bu) (Me2Pir) (HMTO) ( PMe2Ph) and 2.02 equivalents of B (C6F5) 3): 1H-RNM δ 7.06 (s, 1, WCH-t-Bu, 3JWH = 17 Hz), 7.26 (t, 1, Ar-H ), 7.12 (d, 2, Ar-H), 6.93 (s, 2, Ar-H), 6.57 (s, 2, Ar-H), 5.76 (expanded s, 1, Pir-H), 5.44 (extended s, 1, Pir-H), 2.11 (s, 6, Ar-Me), 2.05 (s, 6, Ar-Me), 1.89 (s , 6, Ar-Me), 1.86 (s, 3, Pir-Me), 1.54 (s, 3, Pir-Me), 0.89 (s, 9, WCH-t-Bu); 13C {1H} -RNM: δ 274.2 (WCH-t-Bu, 1JCH = 115 Hz), 157.8, 147.8, 145.9, 137.3, 135.5, 135.3, 131, 4, 130.9, 128.3, 128.2, 125.8, 115.0, 112.3, 110.7, 49.7, 31.7, 21.2, 20.7, 20.6, 17.4, 12.8. 19F-RNM: -135.2 (broad, 1), -136.3 (broad, 1), -161.1 (broad, 1), -165.6 (broad, 1), -166.7 (broad , 1). 11B-RNM: -3 (very wide). Table 11. Crystal data and structure refinement details for W (O) (CH-t-Bu) (B (C6F5) 3 (OHMT) (Me2Pir) (I-6).


[0296] In some embodiments, compounds I-7, I

[0297] We conclude that oxo-tungsten-alkylidene complexes are viable catalysts for the coupling of Z-selective metathesis of terminal olefins. Without being bound by a particular theory, it is believed that the resulting selectivity is caused by the small size of the oxo ligand in relation to OHMT, the low isomerization rate of the initial Z product in relation to the coupling of terminal olefins, and decomposition of the catalyst active under the conditions employed. New synthesis of tungsten alkylidene-oxo complexes
[0298] The original synthesis of W (O) (CH-t-Bu) Cl2 (PMe2Ph) 2 and related bisphosphine complexes was based on the synthesis of a tantalum-neopentylidene complex and transfer of the tantalum to tungsten neopentilidene ligand, as shown below (L is PMe2Ph):

[0299] Ta (CH-t-Bu) Cl2 (PMe2Ph) 2 is prepared from Ta (CH2-t-Bu) 3Cl2, which is synthesized from TaCl5 and Zn (CH2t-Bu) 2 in pentane. For this synthesis, Zn (CH2t-Bu) 2 must be prepared and intensively purified before use. W (O) (Ot-Bu) 4 can be synthesized in modest yield in a reaction between W (O) Cl4 and LiO-t-Bu and isolated by means of sublimation, but again the process is slow and indirect: that is, alkylidene is not prepared in tungsten. Other methods have been tried, including by alkylating W (O) Cl4. However, it has been found that direct alkylation of W (O) Cl4 with lithium, magnesium, aluminum or zinc leads to complex mixtures containing complexes in which the oxo group has been removed from the metal and / or the metal has been reduced. The various oxo-alkyl d0 tungsten complexes that are generally known cannot be synthesized in pure form and good yield through direct alkylation of oxo-tungsten complexes.
[0300] The present invention provides new and improved methods of producing oxo-tungsten-alkylidene complexes from readily available starting material. Non-limiting examples are described herein.
[0301] In some embodiments, W (O) 2Cl2 is prepared on a large scale in a reaction between tungsten hexachloride and hexamethyldisiloxane in dichloromethane. Pale yellow W (O) 2Cl2 (bipi) can be prepared on a large scale basically in one step from WCl6 by adding bipyridine to a solution in W (O) 2Cl2 (DME) dichloromethane (DME = dimethoxyethane) . The addition of 3.7 equivalents of neopentylmagnesium chloride to a solution of 2 in THF results in the formation of dark red solutions. After aqueous aerobic development analogous to that reported by Schrauzer (Zhang, C .; Schlemper, EO; Schrauzer, GN Organometallics 1990, 9, 1.016), W (O) 2 (CH2-t-Bu) 2 (beep) yellow (3a) can be isolated at 70% yield. Similar reactions using PhMe2CH2MgCl led to W (O) 2 (CH2CMe2Ph) 2 (beep) (3b) in 67% yield. The proton spectra of MRI are consistent with 3a, b which have C2V symmetry with the two oxo cis ligands between them and trans for bipi. Treatment of 3a with a mixture containing one equivalent of ZnCl2 (dioxane), slightly less than two equivalents of PMe2Ph and two equivalents of trimethylsilyl chloride (TMSCl) in toluene at 100 ° C for two hours led to the formation of the oxo-tungsten-alkylidene, W (O) (CH-t-Bu) Cl2 (PMe2Ph) 2, hexamethyldisiloxane (TMS2O), neopentane and ZnCl2 (bipi). Double recrystallization of the crude product from a mixture of ether and tetrahydrofuran generated 1a in 45% isolated yield. The neophilidene analog, W (O) (CHCMe2Ph) Cl2 (PMe2Ph) 2 (1b), was prepared in a similar manner and isolated in 39% yield as a yellow solid. As 1a, 1b is a syn alkylidene based on the JCHα value for the alkylidene (126 Hz). The two phosphine ligands are equivalent and remain linked to tungsten on the RNM time scale at 22 ° C with JPW = 333 Hz. The new synthesis of W (O) (CHR) Cl2 (PMe2Ph) 2 1a and 1b complexes consists in three relatively simple steps, starting from tungsten hexachloride, which is a significant improvement over the existing method.

[0302] Without being bound by a particular theory, a mechanism for the above transformation is proposed. It is proposed that the alkylidene formation mechanism in 1a, b involves attacking one of the oxo ligands in W (O) 2 (CH2R) 2 (bipi) (R = t-Bu, CMe2Ph) successively by 2 TMSCl equivalents for generate TMS2O and an intermediate W (O) Cl2 (CH2R) 2 (beep), where CH3R is lost to generate W (O) (CHR) Cl2 (beep). The intramolecular abstraction of a proton in the alkyl group becomes possible after an oxo ligand is replaced by two chlorides, especially in the presence of a ligand that could promote an abstraction in an intermediate of 18 electrons, of seven coordinates. There is a possibility that an abstraction will occur in an intermediate species W (O) Cl (OSiMe3) (CH2R) 2 (bipi), followed by replacement of trimethylsiloxide with chloride by further reaction with TMSCl. The treatment of W (O) 2 (CH2-t-Bu) 2 (bipi) with only 2 equivalents of TMSCl leads to a product mix whose MRI spectra are consistent with the main product being W (O) (CH-t) -Bu) Cl2 (beep). Synthesis of oxo-alkylidene derivatives
[0303] The reaction between 1a and LiOR (LiOR = LiOHIPT, LiOHMT) in benzene at 22 ° C led to the formation of whitish complexes of W (O) (CHt-Bu) Cl (OR) (PMe2Ph) 4a (OR = OHMT ) and 4b (OR = OHIPT), each as a mixture of two syn alkylidene isomers. Phosphine remains bound to tungsten on the MRI time scale at 22 ° C in both 4a and 4b. The addition of LiMe2Pyr at 4a, b led to the isolation of W (O) (CH-t-Bu) (n1 - Me2Pir) (OHMT) (PMe2Ph) (5a) and W (O) (CH-t-Bu) ( n1-Me2Pir) (OHIPT) (5b), both having been characterized by X-ray studies. 11 5b phosphine-free is formed as a result of the greater steric demand of OHIPT versus that of the OHMT ligand. The structure of 5a is a square pyramid with a neopentylidene syn in the apical position and the phosphine trans-linked to the pyrrolidide. The equilibrium constant for phosphine dissociation in 5a was estimated to be 0.015 M at room temperature by means of MRI studies, a value corresponding to 57% dissociation of W (O) (CH-t-Bu) (n1- Me2Pir) (OHMT) free of phosphine being present in a 20 mM solution of 5a in C6D6.
[0304] In some embodiments, the present invention provides methods for the preparation of oxo-tungsten-alkylidene species from a compound having the structure of formula V-b. In some embodiments, the compounds are obtained as 14 and species. In some embodiments, the compounds are obtained as 14 and species without R8. In some embodiments, a compound of formula V-b is 4a. Exemplary methods and prepared compounds are described herein.
[0305] 4a can be used to prepare other oxo-alkylidene species, in addition to 5a, as shown in Scheme 1. Some of the prepared compounds are obtained as 14e without phosphine binder. Layout 1

[0306] The addition of 1 equivalent of 2,5-lithium diphenylpyrrolide to a toluene solution of W (O) (CH-t-Bu) (OHMT) Cl (PMe2Ph) at room temperature led to the formation of W (O ) (CH-t-Bu) (Ph2Pir) (OHMT) yellow (6) in 57% isolated yield. The proton α resonance for the alkylidene resonance in the 1H-NMR spectrum of 6 is found at 9.99 ppm (cf. 9.14 ppm in 5a) with JCH = 124 Hz, which is characteristic of a syn orientation of the alkylidene. Although the alkylidene resonance is slightly increased, the 183W satellites are discernible (JHW = 10 Hz). The resonances for the two protons in the pyrrolidide ring are ample at room temperature, which, without attaching to a particular theory, suggests impeded rotation of the diphenylpyrrolidine ligand or a balance between n1 and n5- coordination modes
[0307] Simple 6 crystals were grown from toluene / pentane solution at -30 ° C. A thermal ellipsoid drawing of the structure is shown in Figure 8. The distance W = O (1.690 (1) Â) is comparable with the bond strength of W = O at 5b (1.665 (3) Â). The pyrrolidide ligand is coordinated in n1 mode with a W-Npir distance of 2.037 (2) Â, versus the binding strength of W-Npir at 5b (2.001 (2) Â). In Mo (NAr) (CH-t-Bu) (n1 - 2.5 - Ph2Pir) (n5 - 2.5 - Ph2Pir), the binding force of Mo-Npir to n1 pyrrolid is slightly longer (2, 1,145 (10) Â) than in 5b. The W-NPir vector in 6 is not located in the plane of the pyrrolidide ligand: that is, the pyrrolidide is inclined so that the angle between the vector W-Npir and the plane is 161.7 °.
[0308] Treatment of 4a with LiN (C6F5) 2 in CH2Cl2 led to the formation of W (O) (CH-t-Bu) [N (C6F5) 2] (OHMT) (PMe2Ph) (7) in 60% of isolated yield. The X-ray structure 7 showed that it is basically a square pyramid with the alkylidene syn ligand in the apical position and the trans phosphine ligand for the amide (Figure 9). The starch nitrogen atom is not flat (the three angles add up to 349.7 (2) °) and one of the ortho fluorides could weakly interact with the trans metal for the alkylidene (W1-F1 = 2.758 (1) A), the which is not uncommon in complexes that contain the perfluordiphenyl starch ligand. The starch ligand could also be considered to be "tilted" out of the plane, as seen for diphenylpyrrolid at 6. The broad resonance of alkylidene at 7 results from the dissociation of phosphine in solution at room temperature. A study of 1H and 31P-MRI at variable temperature of a 74 mM solution of 7 in toluene-d8 showed that phosphine is found on the MRI time scale below -20 ° C (an acute resonance is found at 2, 69 ppm with JPW = 347 Hz), but in toluene at 22 ° C Keq is approximately 0.002 M, that is, approximately 50% of 7 are converted to W (O) (CH-t-Bu) [N- (C6F5) 2] (OHMT) at a concentration of 74 mM. At - 20 ° C, 10 enlarged 19F resonances are observed for 7, which suggests that the N (C6F5) 2 ligand is not rotating freely at -20 ° C.
[0309] The addition of an equivalent of NaOSi (t-Bu) 3 to 4a at room temperature resulted in the formation of phosphine-free W (O) (CH-t-Bu) (OHMT) (Silox) (8) as the single product, according to data from 1H and 31P-RNM. 8 was very soluble in pentane. 8 was prepared from 250 mg of 4 and a solution of it in pentane was exposed to an ethylene atmosphere; the metallacyclobutane complex, W (O) (CH2CH2CH2) (OHMT) (Silox) (9), crystallized as light yellow crystals in 25% isolated yield. It was found that a solution of 0.018 M of 9 in C6D6 under dinitrogen consists of 98% of 9 and 2% of what is proposed as the methylidene complex, W (O) (CH2) (OHMT) (Silox) (δCH2 a 7.77 and 8.93 ppm), formed through the loss of ethylene of 9. Heating a solution of 9 in C6D6 to 70 ° C led to the amplification of the protons of metallocycle and the appearance of free ethylene and amplification of the methylidene signals, consistent with easy ethylene exchange on the WC3 ring on the MRI time scale. Only three metallocycle resonances are observed for W (O) (C3H6) (OHMT) (Silox) in C6D6 (4.10, 2.54 and 193 ppm, 1: 1: 1 ratio); presumably three other resonances are obscured. Three 13C resonances can be attributed to the metal cycle at 43.8, 41.5 and 22.3 ppm. The range of chemical displacements of metallocycle protons and carbons is indicative of square-pyramidal (SP) coordination of the metal center found for W (NAr) [CH2CH (t-Bu) CH2] (Ot-Bu) 2.

[0310] Simple 9 crystals were grown from a mixture of toluene and pentane at -30 ° C. A structural X-ray study confirmed the proposed SP configuration of 9 in which the oxo ligand is in the apical position (Figure 10). To our knowledge, 9 is the first structurally characterized metallacyclobutane derived from an oxoalkylidene and the first unsubstituted molybdocyclobutane or tungstacyclobutane with a high oxidation state that has a square pyramidal geometry (all unsubstituted Mo or W imitated metallocyclobutane complexes have geometries TBP). The bonding forces and bonding angles on the WC3 ring at 9 are identical to those at W (NAr) [CH2CH (t-Bu) CH2] [OCMe2 (CF3)] 2 (within 3G), as shown below. The WC3 ring at 9 is inclined with a dihedral angle of 33.8 ° between the C1-W-C3 and C1-C2-C3 planes, compared to an angle of 33.4 ° in W (NAr) [CH2CH (t- Bu) CH2] [OCMe2 (CF3)] 2. Relatively long W-Cβ distances in SP metallacyclobutane complexes of W (W-C2 = 2,762 (3) Â in 9) led to the proposal that SP metallacyclobutane complexes are further from the transition state to loss of olefin to generate an alkylidene TBP metallocycles
.
[0311] The addition of an LiOHMT equivalent to W (O) (CH-t-Bu) (OHMT) Cl (PMe2Ph) (100 ° C, toluene) leads to the formation of W (O) (CH-t-Bu) ) (OHMT) 2 (10) in good yield. 10 is also prepared in 41% yield isolated by treating W (O) (CH-t-Bu) Cl2 (PMe2Ph) 2 with two equivalents of LiOHMT at 100 ° C in toluene for 48 h. The resonance for the alkylidene proton in the 10 MRI proton spectrum is found at 7.34 ppm with 1JHW = 14 Hz. Three mesityl methyl resonances were observed for the OHMT ligands in the MRI proton spectrum at 22 ° C, consistent with the fact that the OHMT linkers are equivalent, free rotation around the WO bonds, and no rotation around the CC bonds to the central phenyl ring. The two sets of ortho mesityl methyl groups arise from the fact that no plane of symmetry divides the angle C = W = O into 10.
[0312] When a pentane solution of 10 was placed under 1 ethylene atmosphere, a yellow precipitate can be isolated, whose proton spectrum of C6D6 MRI shows that a mixture of W (O) (C3H6) (OHMT) 2 ( 11) and W (O) (CH2) (OHMT) 2 (12) in a 3: 1 ratio is present. We propose that the precipitate is pure 11, but after dissolving in benzene some ethylene is lost from 11 to generate a mixture of 11 and 12 in solution. Only 11 is sufficiently insoluble to precipitate as described. Compound 12 can be isolated in pure form by repeatedly dissolving mixtures of 11 and 12 in toluene, followed by slow removal of the solvent in vacuo
:
[0313] Two methylidene doublet resonances are observed in 1H-NMR spectra of 12 in C6D6 at 8.90 ppm (Hsyn, 1JCH = 160 Hz, JHH = 10 Hz) and 7.85 ppm (Hanti, 1JCH = 140 Hz). The lower JCH value for Hanti is consistent with an agostic interaction of C-Hanti with the metal center. Three resonances of mesityl methyl are found in the proton spectrum of MRI at 22 ° C, as noted above for 10. Compound 12 was found to be stable in solution for at least 24 h at room temperature at a concentration of approximately 20 mM .
[0314] A structural X-ray distribution of 12 confirms that it is a tetrahedral monomeric species of 14 electrons in the solid state (Figure 11). To our knowledge, this is the first structural X-ray study of an oxo-methylidene complex. It was found that the oxo and methylidene ligands are mutually altered in a ratio of 71:29. The disturbance could be resolved and the methylidene protons located in the main component; they have been refined semi-freely with appropriate binding force restrictions (see Support information). The bond strength of W = C (1,895 (8) Â) is similar to the distances M = C in the two structurally characterized methylidene imido complexes 14e of Mo (1,892 (5) Â) and W (1,908 (4) Â) ( Schrock, RR, King, AJ; Marinescu, SC; Simpson, JH; Muller, P. Organometallics 2010, 29, 5,241). The plane of CH2 is inclined approximately 9 ° to the plane of O = W = C, as is also found in the two imido methylidene complexes of Mo and W (by 8 °). The angle of W = C1-H1a (Hanti) (109 (3) °) is less than the angle of W = C1-H1b (Hsyn) (127 (3) °), consistent with an agostic interaction between the CHanti bond and the metal center, and with the lower values of 2JCHanti in relation to the values of 2JCHsyn. The bond strength of W = O (1,694 (5) Â) is comparable to that in W (O) (CH-t-Bu) (Me2Pir) (HYPTO) (1,695 (3) Â, Peryshkov, DV; Schrock, RR; Takase, MK; Muller, P .; Hoveyda, AHJ Am. Chem. Soc. 2011, 133, 20.754). The planes of two phenolate rings of the terfenoxides intersect at an angle of 81.5 ° between them. The almost “perpendicular” relationship of the two OHMT ligands looks like a baseball cover and, without being bound by a particular theory, should prevent the formation of the bis-μ-methylidene intermediate necessary for bimolecular decomposition, although it should not block access from ethylene to metal and the formation of a square pyramidal metalacyclobutane complex 11. Without being limited to a particular theory, the 2,6-terphenoxide ligand contributes to discourage bimolecular decomposition. EXPERIMENTAL General comments.
[0315] All manipulations were carried out in a dry box filled with nitrogen or in an air-free double collector Schlenk line. The solvents were sprayed with nitrogen, passed through activated alumina and stored over 4 Â ° activated Linde molecular sieves. Methylene chloride-d2, benzene-d6, and toluene-d8 were distilled from calcium hydride (CD2Cl2) or sodium cetyl (C6D6, C7D8), and stored on 4 Lin activated Linde molecular sieves. MRI spectra were recorded using Varian spectrometers at 500 (1H), 125 (13C) and 121 (31P) MHz, reported in δ (parts per million) in relation to tetramethylsilane (1H, 13C) or 85% phosphoric acid (31P ), and referenced to the residual 1H / 13C signals of the deuterated solvent (1H (δ): benzene 7.16; methylene chloride 5.32, chloroform 7.26, toluene 7.09, 7.01, 6.97, 2.08; 13C (δ): benzene 128.06; methylene chloride 53.84, chloroform 77.16, toluene 20.43) or external standard 85% phosphoric acid (31P (δ): 0) and hexafluorbenzene ( 19F (δ): -164.9). Midwest Microlab, Indianapolis, Indiana provided the results of the element analysis.
[0316] W (O) (CHCMe3) Cl (HMTO) (PMe2Ph), H (2,5-Ph2Pir), NH (C6F5) 2 were prepared according to reported procedures. H (Silox) was received as a donation from Professor Pete Wolczanski. NaSilox was prepared in the reaction of H (Silox) and NaH in THF. All other reagents were used as received, unless otherwise noted. Synthesis of W (O) 2Cl2 (beep).
[0317] The compound was prepared by a modification of the published procedure. A solution of hexamethyldisiloxane (21.482 g, 132 mmol, 2.1 equivalents) was added dropwise to the solution of tungsten hexachloride (25,000 g, 63.0 mmol) in 250 ml of dichloromethane. A solution of dimethoxyethane (13.058 g, 144.9 mmol, 2.3 equivalents) was added. The mixture was stirred for 2 h at room temperature and during that time it turned dark blue and contained a suspended precipitate. A pale blue solution was obtained after filtering the mixture through Celite. A solution of 2,2'-bipyridine (10,330 g, 66.1 mmol, 1.05 equivalent) in 30 ml of dichloromethane was added, and the mixture was stirred for 30 min. The precipitate was isolated by filtration, washed twice with 50 ml of dichloromethane and dried in vacuo. The pale yellow powder was collected (25.824 g, 58.3 mmol, 92% yield). Anal. calculated for C10H8Cl2N2O2W: C, 27.10; H, 1.82; N, 6.32. Found: C, 26.27; H, 1.86; N, 5.97. Synthesis of W (O) 2 (CH2CMe3) 2 (beep) (3a).
[0318] Compound 3a was prepared in a similar way to the published procedure using W (O) 2Cl2 (beep) instead of W (O) 2Br2 (beep) as a starting material. A cold (-30 ° C) solution of (CH3) 3CCH2MgCl in ether (40 ml, 1.66 M, 3.7 equivalents) was added to an ice-cold suspension (-30 ° C) of W (O) 2Cl2 (beep ) (8,000 g, 18.06 mmol) in 150 ml of THF. The reaction mixture was stirred at room temperature for 1 h. The volatiles were removed in vacuo leaving a dark red residue. After adding water (300 ml), the mixture was periodically stirred with CH2Cl2 (200 ml) in air. The organic fraction gradually changed the color from green to yellow to orange. The mixture was filtered through Celite. The aqueous layer was separated and discarded. The organic layer was washed five times with portions of water (150 ml), dried with anhydrous MgSO4, and concentrated to a volume of 20 ml, causing a yellow solid to form. A portion of hexane (200 ml) was added and the mixture was filtered. The precipitate was recrystallized from dichloromethane / hexane. The solid product was isolated by filtration and dried under vacuum (6.464 g, 12.57 mmol, 70% yield): 1H-RNM (CD2Cl2) δ 9.55 (m, 2, bipi H), 8.39 (m , 2, beep H), 8.15 (m, 2, beep H), 7.58 (m, 2, beep H), 0.94 (s, 18, CH2CMe3), 0.81 (s, 4, CH2CMe3, JWH = 8 Hz); 13C-RNM (CD2Cl2) δ 196.3, 152.0, 150.4, 139.2, 125.8, 123.6, 68.1, 34.9, 33.5. Anal. calculated for C20H30N2O2W: C, 46.71; H, 5.88; N, 5.45. Found: C, 46.79; H, 5.91; N, 5.47. Synthesis of W (O) 2 (CH2CMe2Ph) 2 (beep) (3b).
[0319] The compound was prepared in a manner analogous to that used to prepare 3a. A cold (-30 ° C) solution of (CH3) 2PhCCH2MgCl in ether (100 ml, 0.5 M, 3.7 equivalents) was added to a cold (-30 ° C) suspension of W (O) 2Cl2 (beep) ) (6,000 g, 13.55 mmol) in 80 ml of THF. The reaction mixture was stirred at room temperature for 1 h. The volatiles were removed under vacuum, leaving a dark red residue. After adding water (300 ml), the mixture was periodically stirred with CH2Cl2 (200 ml) in air. The organic fraction gradually changed the color from green to yellow. The mixture was filtered through Celite. The aqueous layer was separated and discarded. The organic layer was washed five times with portions of water (150 ml), dried with anhydrous MgSO4, and concentrated to a volume of 20 ml, causing a pale yellow solid to form. A portion of hexane (150 ml) was added, and the mixture was filtered. The precipitate was recrystallized from chloroform / hexane. The solid product was isolated by filtration and dried under vacuum (5.85 g, 9.16 mmol, 67% yield): 1H-RNM (CD2Cl2) δ 8.95 (m, 2, bipi H), 8.24 (m, 2, beep H), 8.03 (m, 2, beep H), 7.35 (m, 2, beep H), 7.05 (m, 10, CH2CMe2Ph), 1.38 (s, 12, CH2CMe2Ph), 1.06 (s, 4, CHCMe2Ph, JWH = 8 Hz); 13C-RNM (CD2Cl2) δ 154.1, 152.0, 149.9, 138.9, 127.7, 126.0, 125.8, 124.8, 123.6, 68.2, 41.3 , 32.2. Anal. calculated for C30H34N2O2W: C, 56.44; H, 5.37; N, 4.39. Found: C, 56.42; H, 5.44; N, 4.35. Synthesis of W (O) (CHCMe3) Cl2 (PMe2Ph) 2 (1a).
[0320] Compound 3a (3.80 g, 7.39 mmol) was mixed with ZnCl2 (dioxane) (1.74 g, 7.76 mmol, 1.05 equivalent) and PMe2Ph (1.94 g, 14, 04 mmol, 1.9 equivalent) in 40 ml of toluene. The mixture was cooled to -30 ° C, and TMSCl (1.77 g, 16.26 mmol, 2.2 equivalents) was added. The mixture was stirred at room temperature for 30 min and then heated to 100 ° C for 2 h, during which time the color darkened and a precipitate formed. All volatiles were removed under vacuum at 50 ° C. Benzene (40 ml) was added to the dark residue, and the mixture was filtered through Celite. The solvent was evaporated from the filtrate in vacuo, leaving a yellow solid and a brown oil. The residue was stirred with 40 ml of ether for 3 h, during which time the oil disappeared and a yellow solid remained. The solid was recrystallized twice from a mixture of ether and tetrahydrofuran at -30 ° C to produce a yellow crystalline solid (2.03 g, 45% yield). The 1H-RNM spectrum of the product is identical to that reported: 1H-RNM (C6D6) δ 12.10 (t, 1, WCHCMe3, 1JCH = 125 Hz, 3JPH = 4 Hz), 7.65 (m, 4), 6.97 (m, 6), 1.92 (m, 12, PMe2Ph), 0.82 (s, 9, WCHCMe3). Anal. calculated for C21H32Cl2OP2W: C, 40.87; H, 5.23. Found: C, 40.90; H, 5.12. Synthesis of W (O) (CHCMe2Ph) Cl2 (PMe2Ph) 2 (1b).
[0321] The compound was prepared in a manner analogous to that described for 1a. Compound 3b (2.99 g, 4.68 mmol) was mixed with ZnCl2 (dioxane) (1.10 g, 4.91 mmol, 1.05 equivalent) and PMe2Ph (1.22 g, 8.85 mmol, 1.8 equivalent) in 40 ml of toluene. The mixture was cooled to -30 ° C, and TMSCl (1.17 g, 10.76 mmol, 2.3 equivalents) was added. The mixture was stirred at room temperature for 30 min and was heated to 100 ° C for 2 hours, during which time the color darkened and a precipitate formed. The volume of solvent was reduced to approximately 30 ml in vacuo, and 10 ml of pentane was added. The solution was filtered through Celite, and the volatiles were removed in vacuo, leaving a brown oil. The residue was recrystallized twice from a mixture of ether and tetrahydrofuran at -30 ° C to generate a yellow crystalline solid (1.24 g, 39% yield): 1H-RNM (C6D6) δ 12.01 (t, 1 , WCHCMe2Ph, 1JCH = 126 Hz, 3JPH = 4 Hz), 7.68 (m, 4), 7.03 (m, 8), 6.96 (m, 3), 1.94 (t, 6, PMe2Ph ), 1.58 (t, 6, PMe2Ph), 1.27 (s, 6, WCHCMe2Ph); 13C-RNM (C6D6) δ 315.8 (t, WCHCMe2Ph, JPC = 11 Hz), 150.6, 135.1 (t), 131.4 (t), 130.6, 128.75, 128.70 , 128.65, 126.8, 126.1, 51.9, 30.9, 14.7 (td); 31P-RNM (C6D6) δ 4.02 (JPW = 333 Hz). Anal. calculated for C26H34Cl2OP2W: C, 45.97; H, 5.05. Found: C, 46.23; H, 4.99. Synthesis of W (O) (CHCMe3) (Ph2Pir) (OHMT) (6).
[0322] A solution of W (O) (CHCMe3) Cl (OHMT) (PMe2Ph) (300.0 mg, 0.388 mmol) in 10 ml of benzene was added to a portion of solid Li (Ph2Pir) (105.0 mg , 0.466 mmol, 1.2 equivalent). The cloudy reaction mixture was stirred at room temperature for 24 h. The solvent was removed in vacuo to generate a brown oil. The product was extracted into toluene (5 ml) and the mixture was filtered through a bed of Celite. Toluene was removed in vacuo to produce brown oil. A yellow solid precipitated by adding pentane (4 ml) and the resulting suspension was filtered and washed with 5 ml of pentane. The yellow solid was recrystallized from toluene / pentane at -30 ° C: yield of 182.0 mg, 57%; 1H-RNM (C6D6) δ 9.99 (s, 1, WCH-t-Bu, 1JCH = 124 Hz, 2JWH = 11 Hz), 7.24-6.94 (m, 12), 6.89 (s , 2), 6.65 (s, 2), 6.61 (d, 1), 6.46-6.14 (br., 2), 2.22 (s, 6, Ar Me), 2, 18 (s, 6, Ar Me), 2.04 (s, 6, Ar Me), 0.71 (s, 9, WCH-t-Bu); 13C-RNM (C6D6) δ 279.7 (WCH-t-Bu, 1JCW = 201 Hz), 157.4, 137.8, 137.5, 137.3, 136.2, 133.8, 133.5 , 133.1, 131.5, 130.7, 129.4, 129.2, 129.1, 127.1, 126.4, 124.3, 123.1, 113.1, 111.4, 108 , 6, 42.9, 32.1, 21.4, 21.2, 21.1. Anal. calculated for C45H47NO2W: C, 66.10; H, 5.79; N, 1.71. Found: C, 65.93; H, 5.90; N, 1.76. Synthesis of W (O) (CHCMe3) [N (C6F5) 2] (OHMT) (PMe2Ph) (7).
[0323] A solution of W (O) (CH-t-Bu) Cl (OHMT) (PMe2Ph) (252 mg, 0.326 mmol) in 10 ml of dichloromethane was added to a portion of solid LiN (C6F5) 2 (127 mg, 0.358 mmol, 1.1 equivalent). The reaction mixture was stirred at room temperature for 8 h, during which time a white precipitate formed. The solvent was removed in vacuo to generate a brown oil. The product was extracted into toluene (5 ml), and the solvent was filtered through a bed of Celite. Toluene was removed in vacuo to produce yellow oil. The oil was dissolved in a mixture of 1/4 ether and pentane and cooled to -30 ° C. The product was collected as an off-white solid: yield of 230 mg, 65%; 1H-RNM (74 mM in C6D5CD3, 22 ° C) δ 10.21 (br, 1, WCH-t-Bu), 7.25 (m, 2), 7.00 (m, 3), 6.82 (m, 6), 6.64 (br, 2), 2.23 (br, 6, Ar Me), 2.10 (br, 6, Ar Me), 2.04 (br, 6, Ar Me) , 1.20 (br, 6, PMe2Ph), 0.60 (br, 9, WCH-t-Bu); 31P-RNM (74 mM in C6D5CD3, 22 ° C) δ 2.44 (br); 1H- RNM (74 mM in PMe2Ph, -20 ° C) δ 10.37 (br, 1, WCH-t-Bu), 7.20 (m, 2), 6.95 (m, 3), 6, 81 (m, 6), 6.72 (br, 1), 6.54 (br, 1), 2.35 (br, 3, Ar Me), 2.22 (br, 3, Ar Me), 2 , 17 (br, 6, Ar Me), 2.03 (br, 3, Ar Me), 2.00 (br, 3, Ar Me), 1.17 (d, 6, PMe2Ph), 0.52 ( br, 9, WCH-t-Bu); 13C-RNM (74 mM in C6D5CD3, -20 ° C, CF are expected to be weak) δ 297.3 (WCH-t-Bu), 160.1, 139.1, 138.5, 138.0, 137 , 6, 137.1, 136.8, 136.5, 135.0, 134.7, 133.8, 133.4, 133.0, 132.7, 131.9, 130.9, 130.8 , 130.6, 129.7, 128.5, 128.4, 128.2, 120.9, 44.3, 29.8, 22.1, 21.8, 21.4, 21.1, 21 , 0, 20.9, 14.3 (d), 11.4 (d); 31P-RNM (74 mM in C6D5CD3, -20 ° C) δ 2.69 (s, JPW = 347 Hz); 19F-RNM (74 mM in C6D5CD3, -20 ° C) δ -146.18 (br, 1), -146.62 (br, 1), -152.04 (br, 1), -160.78 ( br, 1), -165.66 (br, 1), -167.58 (br, 2), -168.91 (br, 1), -169.09 (br, 1), -174.82 ( br, 1). Anal. calculated for C49H46F10NO2PW: C, 54.21; H, 4.27; N, 1.29. Found: C, 54.50; H, 4.32; N, 1.59. Synthesis of W (O) (C3H6) (OHMT) (Silox) (9).
[0324] A cold (-30 ° C) solution of W (O) (CH-t-Bu) (OHMT) Cl (PMe2Ph) (250.0 mg, 0.323 mmol) in 10 ml of toluene was added to a portion of solid NaSilox (85.2 mg, 0.357 mmol, 1.1 equivalent). The brown reaction mixture was stirred at room temperature for 3 h. The solvent was removed in vacuo to generate a brown oil. The product was extracted into toluene (5 ml), and the mixture was filtered through a bed of Celite. Toluene was removed in vacuo to produce a brown oil. Pentane (3 ml) was added to the oil. The solution was degassed for three successive freeze-pump-thaw cycles, and 1 ethylene atmosphere was added. The mixture was stirred at 0 ° C for 1 h, during which time a yellow crystalline precipitate formed. The precipitate was removed by filtration, washed with 0.5 ml of cold pentane, and collected: yield of 64 mg, 25%. A solution of 0.018 M in C6D6 contained 98% of 4 and 2% of the corresponding methylidene, together with the equivalent amount of ethylene: 1H-RNM (C6D6) δ 7.02-6.90 (m, 7, Ar H), 4.10 (m, 1, WC3H6), 2.54 (m, 1, WC3H6), 2.26 (br s, 12, Ar Me), 2.20 (s, 6, Ar Me), 1.93 (m, 1, WC3H6), 1.05 (s, 27, SiCMe3); 13C-RNM (C6D6) δ 156.6, 136.8 (br), 136.4 (br), 135.0 (br), 134.4 (br), 130.6, 129.2, 128.7 , 124.0, 43.8 (WC3H6), 41.4 (WC3H6), 30.0 (SiCMe3), 23.9 (SiCMe3), 22.3 (WC3H6), 21.4 (br, Ar Me), 21.2 (Ar Me). Anal. calculated for C39H58O3SiW: C, 59.42; H, 7.43. Found: C, 59.20; H, 7.11. Synthesis of W (O) (CHCMe3) (OHMT) 2 (10).
[0325] A solution of W (O) (CHCMe3) Cl2 (PMe2Ph) (200.0 mg, 0.324 mmol) in 10 ml of toluene was added to a solution of LiOHMT (261.6 mg, 0.778 mmol, 2.4 equivalent). The reaction mixture was stirred at 100 ° C for 48 h, and the volatiles were removed in vacuo to generate a brown oil. The product was extracted into toluene (5 ml), and the mixture was filtered through a bed of Celite. Toluene was removed in vacuo to generate a brown oil. The addition of 4 ml of pentane caused a yellow solid to precipitate. The solid was removed by filtration and washed with 3 ml of cold pentane: yield of 124 mg, 41%; 1H- RNM (C6D6) δ 7.34 (s, 1, WCH-t-Bu, 1JCH = 122 Hz, 2JWH = 14 Hz), 6.90 (br s, 4, Ar H), 6.87-6 , 85 (m, 8, Ar H), 6,836.80 (m, 2, Ar H), 2.26 (s, 12, Ar Me), 2.08 (s, 12, Ar Me), 2.03 (s, 12, Ar Me), 0.92 (s, 9, WCH-t-Bu); 13C-RNM (C6D6) δ 253.6 (WCH-t-Bu), 158.5, 137.0, 136.7, 136.5, 134.9, 131.7, 130.7, 128.9, 128.8, 123.0, 41.1, 33.2, 21.6, 21.3, 20.8. Anal. calculated for C53H60O3W: C, 68.53; H, 6.51. Found: C, 68.22; H, 6.53. Synthesis of W (O) (CH2) (OHMT) 2 (12).
[0326] A sample of 11 (60 mg, 0.067 mmol) was dissolved in 1 ml of toluene, and the solvent was removed in vacuo at room temperature. After two additional dissolution / evacuation cycles, a brown oil was obtained. Toluene (0.1-0.2 ml) and pentane (0.3-0.5 ml) were added, and the sample was placed in a freezer at -30 ° C for 2 days. Yellow crystals formed and were separated from the brown mother liquor by decanting: yield of 32 mg, 55%; 1H-RNM (C6D6) δ 8.90 (d, 1, WCHsyn, 2JHH = 10 Hz, 1JCH = 160 Hz), 7.85 (d, 1, WCHanti, 2JHH = 10 Hz, 1JCH = 140 Hz), 6 , 90 (br s, 4, Ar H), 6.89-6.85 (m, 8, Ar H), 6.84-6.80 (m, 2, Ar H), 2.22 (s, 12, Ar Me), 2.00 (s, 12, Ar Me), 1.96 (s, 12, Ar Me); 13C-RNM (C6D6) δ 225.8 (WCH2), 158.1, 137.2, 136.9, 136.7, 134.4, 131.5, 130.0, 128.3, 123.4, 123.0, 21.3, 20.9, 20.8. Anal. calculated for C49H52O3W: C, 67.43; H, 6.01. Found: C, 67.74; H, 6.12. Synthesis of 1-MeO-2,6- (C6F5) 2-C6H3.
[0327] 1-MeO-2,6- [B (OH) 2] 2-C6H3 (700 mg, 3.58 mmol), Pd (PPh3) 4 (165 mg, 0.143 mmol) and K2CO3 (2.47 g , 17.9 mmol) were suspended in a mixture of toluene (12 ml) and ethanol (8 ml). C6F5Br (1.33 ml, 10.73 mmol) was added at room temperature. After reflux for 1 day, the mixture was cooled to room temperature and filtered through a plug of silica and washed with CH2Cl2. Removal of the solvent generated a light yellow oil which was dissolved in a mixture of CH2Cl2 and hexane; colorless crystals formed at -35 ° C; 1.021 g (65%) yield: 1H-RNM (300 MHz, acetone-d6, 20 ° C) δ 7.63 (d, 3JHH = 5 Hz, 2H), 7.48 (t, 3JHH = 5 Hz, 1H), 3.38 (s, 3H, Me); 19F-RNM (282 MHz, acetone-d6, 20 ° C) δ -141.9 (m, 4F, oF), -157.6 (t, 3JFF = 21 Hz, 2F, pF), -165.0 ( m, 4F, mF); 13C {1H} -RNM (125 MHz, acetone-d6, 20 ° C) δ 158.3 (s, 1C), 145.8 (d, 1JCF = 298 Hz, 4C), 142.1 (d, 1JCF = 252 Hz, 2C), 138.8 (d, 1JCF = 250 Hz, 4C), 128.6 (s, 2C), 125.4 (s, 1C), 121.6 (s, 2C), 113.5 (t, 2JCF = 19 Hz, 2C). HRMS (ESI / [M + Na] +) calculated for C19H6F10NaO: 643.0151. Found: 643.0149. Synthesis of HO-2,6- (C6F5) 2-C6H3.
[0328] 1-MeO-2,6- (C6F5) 2C6H3 (552 mg, 1.25 mmol) was dissolved in CH2Cl2 (20 ml). BBr3 (0.238 ml, 2.51 mmol) was added at 0 ° C. The mixture was warmed to room temperature. After 16 hours, water (10 ml) was added to quench the reaction. The organic layer was separated from the aqueous layer and the aqueous layer was extracted with diethyl ether. The organic parts were combined and dried with MgSO4. Removal of the solvent in vacuo generated a white solid which was recrystallized from hexanes to generate colorless crystals; 482 mg (90%) yield: 1H-RNM (300 MHz, CDCl3, 20 ° C) δ 7.42 (d, 3JHH = 8 Hz, 2H), 7.28 (t, 3JHH = 7 Hz, 1H) , 4.92 (br, 1H, OH); 19F-RNM (282 MHz, CDCl3, 20 ° C) δ -139.9 (m, 4F, oF), -154.3 (t, 3JFF = 21 Hz, 2F, pF), -165.0 (m, 4F, mF); 13C {1H} -RNM (125 MHz, CDCl3, 20 ° C) δ 151.3 (s, 1C), 145.0 (d, 1JCF = 250 Hz, 4C), 141.4 (d, 1JCF = 242 Hz , 2C), 138.2 (d, 1JCF = 253 Hz, 4C), 133.6 (s, 2C), 1. 1.7 (s, 1C), 115.0 (s, 2C), 111.2 (t, 2JCF = 19 Hz, 2C). Anal. calculated for C14H4F10O: C, 50.72; H, 0.95. Found: C, 50.96; H, 1.06. Details of the distribution of the X-ray crystal structure.
[0329] Low temperature diffraction data (Φ and ® scans) were collected on a Bruker-AXS X8 Kappa Duo diffractometer coupled to a Smart APEX 2 CCD detector with Mo Ka radiation (À = 0.71073 Â) from a IμS. Absorption corrections and other corrections were applied using SADABS. All structures were solved by direct methods of using SHELXS and refined against F2 in all data by minimum squares of total matrix with SHELXL-97 using established refinement approaches. All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were included in the models in geometrically calculated and refined positions using the mooring model, except for alkylidene, metallocycle and methylidene protons. The coordinates for these hydrogen atoms were taken from the Fourier difference synthesis, and the hydrogen atoms were subsequently refined semi-freely with the help of distance restrictions. The isotropic displacement parameters of all hydrogen atoms were fixed at 1.2 times the Ueq value of the atoms to which they are attached (1.5 times for methyl groups). All altered atoms were refined with the help of similarities in distance and displacement parameters 1,2 and 1,3, as well as rigid binding restrictions for anisotropic displacement parameters.
[0330] W (O) (CH-t-Bu) (Ph2Pir) (OHMT) (6) crystallizes in the triclinic space group with a P1 molecule in the asymmetric unit. The coordinates for the hydrogen atom attached to C1 were taken from the Fourier difference synthesis as noted above.
[0331] W (O) (CH-t-Bu) (N (C6F5) 2) (OHMT) (PMe2Ph) (7) crystallizes in the monoclinic space group P21 / c with a molecule in the asymmetric unit. The coordinates for the hydrogen atom attached to C1 were taken from the Fourier difference synthesis as noted above.
[0332] W (O) (C3H6) (OHMT) (Silox) (9) crystallizes in the triclinic space group P1 with a molecule in the asymmetric unit. The tungsten atom and oxo ligand were modeled as a two-component disorder, and the proportion of occupations was refined to 0.9687 (6): 0.0313 (6). It was also found that the Silox ligand was altered in two positions, and the proportion of occupations was refined to 0.521 (8): 0.479 (8). The anisotropic displacement parameters for silicon and carbon atoms of the Silox group were restricted to be equivalent, in pairs.
[0333] W (O) (CH2) (OHMT) 2 (12) crystallizes in the monoclinic space group P21 / n with a molecule in the asymmetric unit. The tungsten atom, oxo ligand and methylidene were modeled as a two-component disorder, and the proportion of occupations was refined to 0.711 (1): 0.289 (1). The anisotropic displacement parameters for tungsten (W1, W1A), oxo and chloride ligands (C1, O1A and C1A, O1) were restricted to be equivalent, in pairs. The coordinates of the hydrogen atoms attached to C1 were taken from the Fourier difference synthesis as noted above. The hydrogen atoms linked to C1A, the minor component of the disorder, cannot be found in the Fourier difference synthesis and were not included in the model.
[0334] The crystal data has been presented below. Table 12. Crystal data and structure refinement for W (O) (CHCMe3) (Ph2Pir) (OHMT).

Table 13. Crystal data and structure refinement for W (O) (CHCMe3) [N (C6F5) 2] (OHMT) (PMe2Ph).

Table 14. Crystal data and structure refinement for W (O) (C3H6) (OHMT) (Silox).


Table 15. Crystal data and structure refinement for W (O) (CH2) (OHMT) 2.


[0335] Although various modalities of the present invention have been described and illustrated herein, those skilled in the art will easily anticipate various other means and / or structures for carrying out the functions and / or for obtaining the results and / or one or more of the advantages described herein , and each of these variations and / or modifications is considered to be included in the scope of the present invention. More generally, those skilled in the art will readily note that all parameters, dimensions, materials and configurations described herein are exemplary only and that the actual parameters, dimensions, materials and / or configurations will depend on the specific application or applications for which the teachings of the present invention are used. Those skilled in the art will recognize, or be able to verify, using only routine experimentation, many equivalent to the specific modalities of the invention described herein. It should be understood, therefore, that the modalities presented above are presented only as an example and that, within the scope of the appended claims and their equivalents, the invention can be practiced in a different way from the one specifically described and claimed here. The present invention is addressed to each characteristic, system, article, material, kit and / or individual method described herein. In addition, any combination of two or more of these characteristics, systems, articles, materials, kits and / or methods, if these characteristics, systems, articles, materials, kits and / or methods are not mutually inconsistent, is included within the scope of the present invention.

权利要求:
Claims (12)
[0001]
1. Compound characterized by having the formula I:
[0002]
2. Use of the compound, as defined in claim 1, characterized in that it is for the production of polymer greater than 50% CIS.
[0003]
3. Use of the compound, as defined in claim 1, characterized by being for the production of polymer greater than 50% syndiotactic.
[0004]
4. Use of the compound, as defined in claim 1, characterized by being to perform a Z-selective metathesis.
[0005]
Compound according to claim 1, characterized by the fact that R3 is -OR, where R is an optionally substituted phenyl.
[0006]
6. Compound according to claim 5, characterized by the fact that R3 is optionally substituted
[0007]
7. Compound according to claim 6, characterized by the fact that R3 is optionally
[0008]
A compound according to any one of claims 1, 5 to 7, characterized by the fact that R4 is -N (R) 2, in which the two groups R are taken together with nitrogen to form a saturated ring, partially unsaturated or optionally substituted 3-8 membered aryl that has 0-3 additional heteroatoms, not including the N atom of N (R) 2, selected independently of nitrogen, oxygen or sulfur.
[0009]
9. Compound according to claim 8, characterized by the fact that two groups R
[0010]
10. Compound according to claim 1, characterized by the fact that R4 is
[0011]
11. Compound according to claim 1, characterized by the fact that R2 is hydrogen and R1 is -C (Me) 3 or -C (Me) 2Ph.
[0012]
12. Compound according to claim 1, characterized in that it is selected from W (O) (CH-T-Bu) (Ph2Pir) (OHMT), W (O) (CH-T-Bu) (Ph2Pir) (OHIPT ), W (O) (CH-t-Bu) [N (C6F5) 2] (OHMT) (PPhMe2), W (O) (CH-T-Bu) [N- (C6F5) 2] (OHMT), W (O) (CH-T-Bu) (Me2Pir) (DFTO) (PPhMe2), W (O) (CH-T-Bu) (Me2Pir) (DFTO), W (O) (CHCMe2Ph) (Me2Pir) ( DFTO) (PPhMe2), W (O) (CHCMe2Ph) (Me2Pir) (DFTO) and W (O) (CH-T-Bu) [N- (C6F5) 2] (DFTO), where OHMT is 2.6 -di (2,4,6-trimethylphenylphenoxy, OHIPT is 2,6-di (2,4,6-triisopropylphenyl) phenoxy, DFTO is 2,6- di (pentafluorfenyl) phenoxy, Ph2Pir is 2,5-diphenylpyrrol-1 -il, Me2Pir is 2,5-dimethylpyrrol-1-yl.

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法律状态:
2019-06-04| B06T| Formal requirements before examination|

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2019-10-08| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2019-12-03| B06I| Technical and formal requirements: publication cancelled|Free format text: ANULADA A PUBLICACAO CODIGO 6.21 NA RPI NO 2544 DE 08/10/2019 POR TER SIDO INDEVIDA. |

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2020-03-17| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|

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2020-09-01| B09A| Decision: intention to grant|

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2020-12-08| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 07/11/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201161556643P| true| 2011-11-07|2011-11-07|

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US61/556,643|2011-11-07|

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PCT/US2012/063898|WO2013070725A1|2011-11-07|2012-11-07|Tungsten oxo alkylidene complexes for z selective olefin metathesis|

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