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    • 专利摘要:
    HYDROGENATION AND DEHYDROGENATION CATALYST, AND MANUFACTURING AND USE PROCESSES. The present invention relates to complexes useful as catalysts for organic chemical syntheses including hydrogenation and dehydrogenation of unsaturated compounds or dehydrogenation of substrates. The range of hydrogenating substrate compounds includes esters, lactones, oils and fats, resulting in alcohols, diols, and triols as reaction products. The catalysts of the present patent application can be used to catalyze a hydrogenation reaction under solvent-free conditions. The present catalysts also allow the hydrogenation to proceed without added base, and they can be used in place of conventional reduction processes in nailing hydrides of elements of the main group. In addition, the catalysts of the present patent application can catalyze a dehydrogenation reaction under homogeneous conditions and / or without a receptor. As such, the catalysts provided herein can be useful in substantially reducing costs and improving the environmental profile of manufacturing processes for a variety of chemical compounds.
    公开号:BR112014006964B1
    申请号:R112014006964-6
    申请日:2012-08-20
    公开日:2020-11-17
    发明作者:Dmitri Goussev；Denis Spasyuk
    申请人:Dmitri Goussev；Denis Spasyuk；
    IPC主号:
    专利说明:

    Field of the Invention
    [001] The present invention relates to catalysts. More specifically, the present invention relates to catalysts useful in hydrogenation and dehydrogenation reactions. Introduction
    [002] Ester reduction is one of the most fundamental organic reactions and is useful for the synthesis of a variety of useful organic alcohols. The reduction of esters is usually performed using hydride reagents of the main group, such as LÍAIH4, or using molecular hydrogen. The use of hydride reducing reagents is inconvenient and expensive, especially on a large scale; in addition, this approach generates large amounts of chemical waste. The hydride reduction method can also be dangerously exothermic in the cooling phase and can be difficult to control. Catalytic reduction of esters under hydrogen gas is, in all respects, a very attractive "ecological" alternative to classic hydride reduction.
    [003] A key aspect of ester reduction with molecular hydrogen is the catalytic system used in the process that can quickly bind and divide molecular hydrogen to generate a transition metal hydride. The development of highly efficient and useful catalysts and catalytic systems for hydrogenation of lactones, esters, oils and fats is an important need in chemistry. In particular, the development of hydrogenation processes operating in the temperature range of 20 to 100 ° C using less than 1000 ppm (0.1 mol%) of catalyst under relatively low pressure of H2 (1 - 50 bar) is highly desirable. Among the few catalysts and catalytic systems capable of converting esters and lactones to alcohols and diols under hydrogen gas, those currently most useful and efficient are transition metal complexes, such as ruthenium, with bidentified phosphine-amine or phosphine-imine binders four-toothed as described in Publication No. 2010/0280273 A1 and in Angew. Chem. Int. Ed. 2007, 46, 7473, incorporated herein by reference. Typical ruthenium catalyst loads of 500-1000 ppm (0.05 - 0.1 mol%) are used, however, the great disadvantage of such methods is the need for a large amount of base (5-10% in mol) mol), like NaOMe, thus reducing the selectivity of the product and generating large amounts of chemical residues, due to the need for product neutralization and extensive purification. In addition, without hydrogenation of naturally occurring esters, for example, flat oils such as olive oil, to generate unsaturated fatty alcohols, it has been reported with ruthenium catalysts. Fatty alcohols behave like nonionic surfactants, due to their amphiphilic nature. They find use in emulsifiers, emollients and thickeners in the food and cosmetics industries, and as industrial solvents. Fatty alcohols are also very useful in the production of surfactants and detergents, and they have a potential in the production of biodiesel.
    [004] The development of ecological chemical processes and the use of biomass for hydrogen production has attracted a lot of attention in recent years. Significant progress in the dehydrogenation of bioalcohols (mainly ethanol) has been achieved with heterogeneous catalysts, however, at the cost of using drastic reaction conditions, such as high temperature (> 200 ° C) and pressure. Therefore, designing well-defined homogeneous catalysts for the dehydrogenation of alcohols in mild conditions represents an important scientific and practical objective.
    [005] Little progress has been made in the area of dehydrogenation without primary alcohol acceptors since Cole-Hamilton and colleagues demonstrated ethanol dehydrogenation catalyzed by [RuH2 (N2) (PPh3) 3], where an excess of NaOH, high temperature (150 ° C) and an intense light source were needed to reach TOF = 210 h-1, after two hours (D. Morton, DJ Cole-Hamilton, ID Utuk, M. Paneque-Sosa, M. Lopez-Poveda, J. Chem. Soc. Dalton Trans. 1989, 489; D. Morton, D. Cole-Hamilton, J. Chem. Soc. Chem. Common. 1988, 1154; and D. Morton, DJ Cole-Hamilton, J. Chem. Soc Chem. Commun. 1987, 248). In recent years, several new homogeneous catalysts for dehydrogenative coupling without primary alcohol acceptors have been developed and studied, such as the systems published by Milstein and collaborators (for a review, see: D. Milstein, Top. Catai. 2010, 53, 915 ). However, all of these new catalysts are inactive at temperatures below 100 ° C, for example, for the conversion of ethanol and propanol to hydrogen and ethyl acetate and propyl propionate, respectively.
    [006] Therefore, there is still a need for efficient metal catalysts for the hydrogenation of esters, lactones, and fats and oils derived from natural sources, which can operate under free base conditions and using relatively low reaction temperature and hydrogen pressure. There is also a need for catalysts capable of efficient alcohol dehydrogenation under mild, and preferably neutral, reaction conditions, for the ecological production of esters and lactones from alcohols and diols, respectively, accompanied by the formation of hydrogen gas.
    [007] The information above is provided for the purpose of disclosing information that the applicant believes may have relevance to the present invention. No admission is necessarily intended, nor should it be interpreted that any preceding information constitutes the state of the art against the present invention. Brief Description of the Figures
    [008] For a better understanding of the present invention, as well as other aspects and additional features of it, reference is made to the following description, which should be used in conjunction with the attached drawings, where:
    [009] Figure 1 is an ORTEP diagram for complex 1, thermal ellipsoids are at 50% probability (hydrogen atoms are omitted for clarity); and
    [0010] Figure 2 is an ORTEP diagram for complex 2, thermal ellipsoids are at 50% probability (hydrogen atoms are omitted for clarity).
    [0011] Figure 3 is an ORTEP diagram for complex 7, thermal ellipsoids are at 50% probability (hydrogen atoms, except NH, are omitted for clarity). Description of the Invention
    [0012] Unless otherwise defined, all technical and scientific terms used in this document have the same meaning as commonly understood by an individual versed in the technique to which this invention belongs.
    [0013] As used in this specification and claims, the singular forms "one (a)" and "the (a)" include references in the plural, unless clearly stated otherwise.
    [0014] The term "comprising", as used in this document, will be understood to mean that the following list is exhaustive and may or may not include any other appropriate additional items, for example, one or more additional features, components and / or ingredients as appropriate.
    [0015] As used here, "heteroatom" refers to non-hydrogen and non-carbon atoms, such as, for example, O, S and N.
    [0016] As used herein, "alkyl" means a hydrocarbon group consisting solely of carbon and hydrogen atoms in simple bond, for example, a methyl or ethyl group.
    [0017] As used here, "alkenyl" means a hydrocarbon moiety that is linear, branched or cyclic and comprises at least one carbon to carbon double bond. "Alquinyl" means a hydrocarbon fraction that is linear, branched or cyclic and comprises at least one carbon to carbon triple bond. "Aryl" means a fraction including a substituted or unsubstituted aromatic ring, including fractions of heteroaryl and fractions with more than one conjugated aromatic ring; optionally, it can also include one or more non-aromatic rings. "Aryl Cs to Cs" means a fraction including a substituted or unsubstituted aromatic ring, having 5 to 8 carbon atoms in one or more conjugated aromatic rings. Examples of aryl fractions include phenyl.
    [0018] "Heteroaryl" means a fraction including a substituted or unsubstituted aromatic ring, having 4 to 8 carbon atoms and at least one heteroatom in one or more conjugated aromatic rings. As used herein, "heteroatom" refers to non-hydrogen and non-carbon atoms, such as, for example, O, S and N. Examples of heteroaryl fractions include pyridyl, furanyl and thienia.
    [0019] "Alkylene" means a divalent alkyl radical, for example, -CfH2f- where f is an integer. "Alkenylene" means a bivalent alkenyl radical, for example, -CHCH-.
    [0020] "Substituted (a)" means to have one or more substituting fractions, whose presence does not interfere with the desired reaction. Examples of substituents include alkyl, alkenyl, alkynyl, aryl, aryl halide, heteroaryl, cycloalkyl (non-aromatic ring), Si (alkyl) 3, Si (alkoxy) 3, halo, alkoxy, amine, alkylamine, alkenylamine, amide, amidine , hydroxyl, thioether, alkylcarbonyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, carbonate, alkoxycarbonyl, aminocarbonyl, alkylthiocarbonyl, phosphate, phosphate ester, phosphonate, phosphinyl, sulfate, aryl, sulfateylate, aryl, sulfate sodium, sulfate, sulfonate, sulfamoyl, sulfonamide, nitro, nitrile, azide, heterocyclyl, ether, ester, fractions containing silicone, thioester or a combination thereof. Substituents can be replaced themselves. For example, an amine substituent can be mono or independently substituted by additional substituents defined above, such as alkyl, alkenyl, alkynyl, aryl, aryl halide and heteroaryl cycloalkyl (non-aromatic ring).
    [0021] As used in this document, the term "pY" is used to indicate that a ligand is functioning as a bridge ligand, where a single atom is bridged between two metal atoms. The superscript "Y" denotes the atom that bridges the two metal atoms. For example, the term "pN" is used to indicate that a ligand (or ligands) in a complex includes a nitrogen atom that bridges two metal atoms.
    [0022] The present application provides a catalyst that is useful in a catalytic hydrogenation (reduction) process. The process is useful in hydrogenating, for example, C3-Cn substrates (n = 4-200) having one or more ester or lactone groups to allow the corresponding alcohol, diol or triol products. Thus, the present application further provides a practical method of reduction that can be used in place of the reduction of hydride main group to obtain alcohols, diols or triols in a simple, efficient and "ecological" way, preferably using reaction conditions free of base. The catalyst of the present application is also useful in a catalytic dehydrogenation process, which can be a homogeneous dehydrogenation process. Catalyst
    [0023] The processes described here are carried out in the presence of a transition metal complex having a tridentated ligand LNN '.
    [0024] In accordance with one aspect, a tridentated LNN 'linker is provided comprising, in sequence, a phosphorus, sulfur, nitrogen or carbon group L, an amine or imine group N and a heterocycle group N'.
    [0025] In accordance with one embodiment, a compound of Formula I is provided
    where: L is a phosphine (PR1R2), a sulfide (SR1) or a carbene group (CR1R2); each Y is independent of an atom of C, N or S, where at least two Y are C; the dotted lines, simultaneously or independently, represent single or double bonds; R1 and R2 are each, independently, H, or a linear C1-C20 alkyl, a branched C3-C20 alkyl, a C3-C8 cycloalkyl, a C2-C8 alkenyl, a C5-C20 aryl, each of which can be optionally replaced; or, when obtained together, R1 and R2 may, together with L to which they are attached, form a saturated or partially saturated ring; R3 and R4 are each, independently, H, or a linear C1-C6 alkyl, a C3-C8 branched alkyl, a C3-C8 cyclic alkyl, a C2-C8 alkenyl, a Cs-Ce aryl, each of which prunes optionally be replaced; or R3 and R4 can join to form a saturated heterocycle; R5 is H, a linear C1-C6 alkyl, a C3-C branched alkyl, a C3-C8 cyclic alkyl, a C2-C8 alkenyl, or a Cs-Cs aryl, each of which can be optionally substituted; or R5 and R4 can come together to form a saturated heterocycle; each X is independently H, a linear C 1 -C alkyl, a C 3 -C 8 branched alkyl, a C 3 -C 8 cyclic alkyl, a C 2-C 8 alkenyl, or a Cs-Ce aryl, each of which can be optionally substituted ; or OR, F, Cl, Br, I or NR2; or when obtained together, two of the X groups may together form an optionally substituted, saturated, partially saturated heteroaromatic or aromatic ring; R is H, a linear C1-C20 alkyl, a branched C3-C20 alkyl, a C3-C8 cycloalkyl, a C2-C8 alkenyl, or a Cs-Ce aryl, each of which can be optionally substituted; each is neither independently 1 or 2; k is 1 or 2; ez is 0 or 1.
    [0026] According to one embodiment, R3 and R4 are each, independently, H, or C1-Cs linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, Ci-Cβ alkenyl, Cs-Ce aryl, each one of which can be optionally substituted, or OR or NR2; and R5 is H, a linear C-i-Ce alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C3-C8 alkenyl, or Cs-C8 aryl, each of which can be optionally substituted, either OR or NR2. In a preferred embodiment, R4 and R5 are both H.
    [0027] According to another modality, each Y is C. According to another modality, k is 2, and each X is H. According to a preferred modality, L is a phosphene.
    [0028] In accordance with one embodiment, the compound of Formula I is

    [0029] According to another aspect, a Formula II or III complex is provided
    where: each Z is, independently, a hydrogen or halogen atom, a Ci-Ce alkyl, a hydroxyl, or a Ci-Ce alkoxy, a nitrosyl group (NO), CO, CNR, or PR3, where R it is an alkyl or an aryl, PMes or PPhs; M is a transition metal; and each LNN 'is a coordinated linker which is a compound according to any one of claims 1-7.
    [0030] According to one embodiment, M is a group 7 metal, a group 8 metal or a group 9 metal. According to a preferred embodiment, M is Ru or Os.
    [0031] According to another embodiment, the complex comprises the ligand LNN ', where LNN' is

    [0032] According to another modality, the complex has the structure of
    where M is as defined above.
    [0033] In a preferential modality, the complex has the structure of any one of


    [0034] According to another aspect, a process for dehydrogenating a substrate is provided comprising treating the substrate with a catalytic amount of a complex as described. In one embodiment, the substrate is a compound of Formula IV

    [0035] wherein R9 is a linear C1-20 alkyl, a branched C3-20 alkyl, a C3-20 cycloalkyl, or an aryl, any of which can be optionally substituted.
    [0036] According to another aspect, a tridentated ligand LNN 'with formula I, R4 is H, a substituted or unsubstituted C3-C8 linear, branched or cyclic alkyl or alkenyl, a substituted or unsubstituted aromatic group Cs- Cs, and a linear, branched or cyclic substituted or unsubstituted Cs-Cs alkyl or alkenyl, a substituted or unsubstituted Cs-Cs aryl.
    [0037] In one embodiment, the heterocycle group N 'of Formula I, where k is 1 or 2, the nitrogen heterocycle N' is optionally substituted and contains Y atoms of carbon, nitrogen, oxygen, or sulfur. A preferred example of the N 'heterocycle is the group C2 - pyridyl, C5H4N.
    [0038] In another specific modality, L is an N-heterocyclic carbene. In another specific modality, L is a phosphene.
    [0039] Some specific examples of tridentated LNN 'ligands are:

    [0040] The tridentate ligand LNN 'described above can be synthesized using standard procedures. For example, the binder can be obtained by condensing optionally substituted aldehyde 2-picolyl (2-CHO-Py) with an aminophosphine or an optionally substituted thioamine. Reduction of the imine product by NaBHzi, AI (tBu) 2H or any other reducing reagents known in the art will lead to the LNN 'ligand of Formula I.
    [0041] The tridentate binders described herein have a relatively low cost of production. The reduced cost is at least partly the result of using cheaper chemicals, as well as surprisingly high efficiency of binder synthesis. Production of these ligands is already an order of magnitude cheaper than other examples of tridentate ligands used in catalyst complexes in the literature.
    [0042] According to another aspect, complexes of General Formulas II and III are provided:

    [0043] where LNN 'is the tridentate ligand of Formula I and a is equal to 2 or 3. Each Z represents, simultaneously or independently, a hydrogen or halogen atom, a C 1 -C 6 alkyl radical, a hydroxyl group or a Ci-Cβ alkoxy radical, a group of nitrosyl (NO), CO, CNR (R = Alkyl, Aryl), PMea or PPhae M is a transition metal. The complexes as described in this document can exist in neutral and cationic forms.
    [0044] According to one embodiment, the transition metal M is preferably a metal of groups 7 (manganese group), 8 (iron group) and 9 (cobalt group). In a preferred embodiment, the transition metal is Ru or Os.
    [0045] In one embodiment, the Formula II complex can be prepared by reacting the Formula I LNN 'ligand with a metal precursor, such as those known in the art. Preferably, the metal precursor is a ruthenium or osmium compound, including, for example, the following formulas: RuHCI (CO) (AsPh3) 3, RuCl2 (CO) (AsPh3) 3, OsHCI (CO) (AsPh3) 3 , OsCI2 (CO) (PPh3) 3, RuHCI (CO) (PPh3) 3, OsCI2 (CO) (AsPh3) 3, [RuCI2 (p-cymene)] 2, RuCI2 (CO) (PPh3) 3; OsHCI (CO) (PPh3) 3; [OsCI2 (p-cymene)] 2; RuCI2 (CO) (p-cymene), OsCI2 (CO) (p-cymene), RuCI2 (CO) (DMF) (PPh3) 2, [lrCI (COD)] 2, [lrCI (COE) 2] 2, lrHCI2 (PPh3) 3, lrH2CI (PPh3) 3, lrHCI2 (AsPh3) 3, or lrH2CI (AsPh3) 3. The reactions can be carried out in several organic solvents, such as, but not limited to, toluene, xylene, benzene, diglyme, DMF or DME.
    [0046] According to another modality, the transformation of a Formula II complex into a Formula III complex can be achieved using a base. Non-limiting examples of suitable bases include group I salts (for example, Li, Na, K) of alkoxides, such as t-butoxide and amides, such as N (TMS) 2. A specific example of an acceptable base is potassium t-butoxide. In certain non-limiting examples, the base has a pKa> 11. Additional non-limiting examples of suitable bases are group I or ammonium salts of hydroxides, alcoholates, alkaline carbonates, amides, siliconates, hydrides, borohydrides, aluminum hydrides, where the group I salt is Li, Na, K or ammonium salts of the formula NR4, and R is alkyl, aryl or H.
    [0047] Complexes of Formulas II and III can be prepared before hydrogenation or in situ using the bases above. Preparation of complexes of Formula II and III can be carried out in various solvents, such as, but not limited to THF, Et2O, toluene, benzene, diglyme, DMF or DME or any other suitable solvents known to the person skilled in the art.
    [0048] Exemplary complex structures 1-9 are shown below:

    [0049] In another aspect, a process is provided for the production of ethyl acetate comprising treating ethanol with a catalytic amount of a complex as described in this document. In one embodiment, the process is a homogeneous process. In another embodiment, the process does not require a hydrogen acceptor. Hydrogenation Process
    [0050] The present application additionally provides a catalytic hydrogenation process. The catalyst complexes of Formulas II and Hl, described above, have been found to show high selectivity for reducing ester groups in the presence of C = C double bonds. This provides a useful way to derive unsaturated alcohols from natural products such as, but not limited to, olive oil or canola oil, under mild reduction conditions.
    [0051] In one embodiment, an ester hydrogenation process using metal catalysts based on the LNN 'ligand of Formula I is provided. According to a specific embodiment, the substrates are composed of the following formulas:

    [0052] The term "substrate" as used in this document and as commonly understood refers to the reagent that will be converted into a product during a catalytic reaction. Groups G1 and G2, simultaneously or independently, represent an optionally substituted, linear, branched C1-C40 or cyclic C3-C40 aromatic, alkyl or alkenyl group. In addition, it is possible to mention a situation when G1 and G2 together form a saturated or unsaturated radical C4-C40. The hydrogenation reaction substrate can be any organic compound containing one, or more, than a carboalkoxy group. In this respect, natural fats, such as olive oil, canola, corn, peanuts, palm and other vegetable oils are useful substrates that can be reduced to form an alcoholic mixture.
    [0053] The reduction or hydrogenation reaction proceeds, in general, according to one of the reaction regimes below:

    [0054] where Gi and G2 are independently selected from any optionally substituted hydrocarbon group. For clarity, where several Gi substituents occur on the same molecule, it is understood that each of these substituents may be a different optionally substituted hydrocarbon.
    [0055] When the substrate is a monoester or a lactone, the products are alcohols or a diol, respectively. Naturally occurring triglycerides, oils and fats can be reduced to corresponding glycerol and fatty alcohols.
    [0056] According to an embodiment of the invention, the process of catalytic reduction of esters involves the use of at least one of the metal complexes 1 or 2, hydrogen pressure and, optionally, a base and a solvent. The base may be necessary in these cases when the metal catalyst 1 contains one or more halogen atoms attached to the metal. The base treatment can be done before the reduction or in situ, adding the base to the reaction mixture during hydrogenation. The catalysts and pre-catalysts of this invention can be used in a wide concentration range, preferably between 10-1000 ppm, and loads of 500 ppm or less are particularly preferred. The preferred amount of the catalyst will depend, as is known to those skilled in the art, on the type of substrate, and the increased catalyst load should result in faster hydrogenation. The temperature at which the hydrogenation can be carried out is between 0 ° C and 150 ° C, more preferably in the range of 50 ° C and 100 ° C, and, as is known to those skilled in the art, the reaction rate will increase with increasing reaction temperature. The hydrogenation reaction requires an H2 gas pressure and must be carried out in a suitable pressure vessel. The surface area of the reactor, as well as the hydrogen pressure, as is known to those skilled in the art, can considerably influence the reaction rate. The higher the hydrogen pressure and the surface area of the reactor, the faster the rate of hydrogenation reaction. It is possible to quote the hydrogen pressure in the range of 10-200 Bar. Once again, the person skilled in the art is able to adjust the pressure depending on the catalyst load and the dilution of the substrate in the solvent. As examples, typical pressures of 5 to 50 bar (5 to 50 X 105 Pa) can be mentioned.
    [0057] It should be understood, however, that the catalyst complexes described herein are also useful for catalyzing the hydrogenation of substrates, including different functional groups of esters. The table below provides a non-limiting list of substrates and corresponding products that can be formed from a catalytic hydrogenation reaction using a Formula II or III catalyst.


    [0058] The present application further provides a catalytic dehydrogenation process using the catalyst complexes of Formulas II and III. For example, this catalyst or pre-catalyst is suitable for dehydrogenation of C2-Cn alcohols (n = 4-200), having one or more -CH2OH groups, thus providing hydrogen gas and corresponding esters or lactones, according to the following scheme. In one embodiment, this process is a homogeneous dehydrogenation process, which can be used in place of existing heterogeneous techniques, preferably using free base reaction conditions and avoiding high reaction temperatures.

    [0059] In this way, one embodiment provides an alcohol dehydrogenation process using metal catalysts based on the LNN 'linker of Formula I. According to one embodiment of the invention, the substrates are composed of the following formulas:

    [0060] In this modality, the R groups, simultaneously or independently, represent an aromatic, alkyl or alkenyl linear, branched C1-C40 or cyclic C3-C40 group, optionally substituted. In addition, it is possible to mention a situation when R is a saturated or unsaturated cyclic radical C4-C40- This implies that the substrate can be any organic compound containing one, or more than one, hydroxyl group (-OH). When the substrate is an alcohol or a diol, the products are a monoester or a lactone, respectively.
    [0061] According to one modality, the dehydrogenation process without catalytic acceptors implies the use of at least one of the metallic complexes of Formulas II or III and (optionally) the use of a base and a solvent. The base may be necessary in these cases when the Formula II metallic catalyst contains one or more halogen or alkoxy (-OR) groups attached to the metal. The catalyst can be treated with base before mixing with the substrate or in situ, adding the base to the reaction mixture during dehydrogenation. The catalysts and pre-catalysts described herein can be used in a wide concentration range, preferably between 10-1000 ppm, and fillers of 1000 ppm or less are particularly preferred. The preferred amount of the catalyst will depend, as is known to those skilled in the art, on the type of substrate, and the increased catalyst load should result in faster dehydrogenation. The temperature at which dehydrogenation can be carried out is between 0 ° C and 200 ° C, more preferably in the range of 50 ° C and 150 ° C, and, as is known to those skilled in the art, the reaction rate will increase with increasing reaction temperature. The dehydrogenation process can generate an H2 gas pressure, in which case it can be performed in a suitable pressure vessel, if necessary, equipped with a pressure release valve.
    [0062] It should be understood, however, that the catalyst complexes described herein are also useful for catalyzing the dehydrogenation of substrates, including functional groups other than alcohols. The table below provides a non-limiting list of substrates and corresponding products that can be formed from a catalytic dehydrogenation reaction using a Formula II or III catalyst.

    [0063] aH2 is also a by-product of these reactions. It is released from the reaction as H2 or transferred to an acceptor.
    [0064] As indicated above, a by-product of dehydrogenation reactions is H2. Thus, the present application further provides a process for the production of H2. The process can conveniently make use of readily available substrates in a simple catalytic dehydrogenation process under relatively mild conditions to generate H2.
    [0065] To obtain a better understanding of the invention described in this document, the following examples are established. It should be understood that these examples are for illustrative purposes only. Therefore, they should not limit the scope of this invention in any way. EXAMPLES
    [0066] Unless otherwise stated, all manipulations were performed under an inert gas (argon or nitrogen) in glove boxes (gloveboxes) or using standard Schlenk techniques. The NMR spectra were recorded on a Varian Unity Inova 300 MHz spectrometer. All 31P chemical shifts are related to 85% H3PO4. The chemical shifts of 1H and 13C were measured in relation to solvent peaks, but are reported in relation to TMS. Osθ4 and RuCl3-3H2O were purchased from Pressure Chemicals. All other anhydrous grade chemicals and solvents went with Aldrich and Alfa Aesar. Commercial anhydrous grade ethanol was further distilled by sodium metal and stored in the argon glove box. (NEt4) 2θsClβ, RuHCI (CO) (AsPh3) 3, OsHCI (CO) (AsPh3) 3, RuCl2 (PPh3) 3, RuCI2 (CO) (DMF) (PPh3) 2 were prepared according to the previously reported methods. (Gusev, DG, Dolgushin, FM, Antipin, M. Yu. Organometallics 2001, 20,1001; Spasyuk, D., Smith, S., Gusev, DG Angew. Chem. 2012, 51, 2772-2775; Shaw, AP , Ryland, BL, Norton, JR, Buccella, D., Moscatelli, A. Inorg. Chem. 2007, 46, 5805-5812; Rajagopal, S., Vancheesan, S., Rajaram, J., Kuriacose, JCJ Mol. 1983, 22, 131-135, incorporated herein for reference). Example 1 - Synthesis of PyCH2NH (CH2) 2N (fPr) 2
    [0067] 2-aminoethyl diisopropylamine (6.32 g, 0.044 mmol) was added to the 2-picolyl aldehyde (4.70 g, 0.044 mmol) and the mixture was stirred for 1 h. The imine obtained was diluted in methanol (15 ml) and NaBH4 (1.66 g, 0.044 mmol) was added depending on the portion over 1 h. Then, all volatile compounds were removed in vacuo and the residue was redissolved in 20 ml of dichloromethane. The solution was filtered through a short pad (3x2 cm) of AI2O3. The aluminum oxide was then washed with 10 ml of dichloromethane and the collected filtrate was evaporated and dried under vacuum for 1 h. The product was obtained as a yellow oil (8.41 g, 90%).
    [0068] 1H NMR (300 MHz, CDCI3) δ = 8.47 (ddd, J = 4.8, 1.8, 0.9 Hz, 1H), 7.73 (td, J = 7.6, 1 , 8 Hz, 1H), 7.39 (d, J = 7.8 Hz, 1H), 7.21 (ddd, J = 7.5, 4.9.1.2 Hz, 1H), 3.77 (s, 2H), 3.33 (br „1H, NH), 2.97 (sep, J = 7.0, 2H; CH), 2.48 (m, J = 2.5 Hz, 4H, CH2 ), 0.92 (d, J = 6.6 Hz, 12H; 4xCH3). 13C NMR ([D6JDMSO) δ = 160.62 (s, 1C; Py), 148.75 (s, 1C; Py), 136.33 (s, 1C; Py), 121.75 (s, 1C; Py ), 121.65 (s, 1C; Py), 54.71 (s, 1C; CH2), 49.23 (s, 1C; CH2), 47.65 (s, 2C; CH), 44.14 ( s, 1C; CH2), 20.72 (s, 1C; 4XCH3). Example 2 - Synthesis of RyCH2NH (CH2) 2P (/ Pr) 2
    [0069] 2-Picolyl aldehyde (1.66 g, 0.0155 mmol) in 10 mL of THF was added to a 10% solution by weight of 2- (di - / - propylphosphino) ethylamine in THF (26, 0 g, 0.0162 mmol) and the mixture was stirred for one hour. The obtained imine was then treated with diisobutyl aluminum hydride (22.7 mL, 1.5 M in toluene, 0.0341 mmol) for one hour (Caution !!! Exothermic reaction!) And left for stirring for one hour. After that time, the solution was cooled with 1 mL of water (Caution !!! Exothermic reaction!) And the obtained suspension was filtered through a short pad (3X2 cm) of basic alumina. The solids were washed with THF (3 x 10 mL) and the collected filtrate was evaporated and dried under vacuum for 3 hours. The product was obtained as a yellow oil (2.84 g, 73%).
    [0070] 31P {1H} NMR ([D6] Benzene) δ = -1.0 (s). 1H NMR ([D6] Benzene) δ = 8.49 (dt, J = 4.7, 1.8 Hz, 1H; Py), 7.15 - 7.13 (m, 1H; Py), 7.09 (td, J = 7.7, J = 1.8 Hz, 1H; Py), 6.64 (ddd, J = 7.0.4,9,1.7 Hz, 1H; Py), 3.93 (s, 2H; PyCH2), 2.81 (m, 2H; NCH2), 1.78 (br. s, 1H; NH), 1.65 - 1.35 (m, 4H; PCH and CH2P), 1 .01 (dd, J = 13.8, 7.1 Hz, 6H; CH3), 0.96 (dd, J = 10.8, 7.0 Hz, 6H; CH3). 13C {1H} NMR ([D6] Benzene) δ = 161.37 (s, 1C; Py), 149.49 (s, 1C; Py), 135.85 (s, 1C; Py), 121.92 ( s, 1C; Py), 121.60 (s, 1C; Py), 55.72 (s; 1C; NCH2), 49.12 (d, J (CP) = 24.9 Hz, 1C; NCH2), 23.72 (d, J (CP) = 13.5 Hz, 2C; PCH), 23.37 (d, J (CP) = 19.3 Hz, 1C; PCH2), 20.29 (d, J ( CP) = 16.5 Hz, 2C; CH3), 18.93 (d, J (CP) = 9.9 Hz, 2C; CH3). Example 3 - Synthesis of trans-OsHCI (CO) [PyCH2NH (CH2) 2P (/ Pr) 2]
    Complex 1
    [0071] A flask containing a mixture of OsHCI (CO) (AsPh3) 3 (5.94 g, 5.57 mmols) and PyCH2NH (CH2) 2P (/ Pr) 2 (1.27 g, 5.06 mmols) in 15 mL of diglyme was placed in an oil bath preheated to 160 ° C and stirred for one hour, providing a dark red solution. After cooling to room temperature, the mixture was diluted with 4 ml of diethyl ether, and the flask was stored overnight in a freezer at 18 ° C. The precipitated product was filtered, washed with diethyl ether (3x3 ml) and dried under vacuum for 3 h to generate a brown crystalline solid. Yield: 1.81 g (71%).
    [0072] 31P {1H} NMR ([D2] DCM) δ = 48.41 (s) .1H {31P) NMR ([D2] DCM) δ = 9.00 (d, J = 5.5 Hz, 1H , Py), 7.68 (td, J = 7.8, 1.5 Hz, 1H, Py), 7.28-7.16 (m, 1H, Py), 4.61 (dd, J = 14 , 3, 4.4 Hz, 1H, PyCH2), 4.12 (br. T, J = 12.0 Hz, 1H, NH), 3.93 (dd, J = 14.2, 11.6 Hz, 1H, PyCH2), 3.67 - 3.58 (m, 1H, NCH2), 2.73 - 2.53 (m, 1H, NCH2), 2.46 (sep, J = 14.7, 7.4 Hz, 1H, PCH), 2.37 (dd, J = 15.0, 4.0 Hz, 1H, CH2P), 2.11 (sept, J = 6.9 Hz, 1H, PCH), 1.77 (td, J = 14.6, 5.8 Hz, 1H, CH2P), 1.35 (d, J = 7.4 Hz, 3H, CH3), 1.21 (d, J = 7.2 Hz, 3H, CH3), 1.09 (d, J = 6.9 Hz, 3H, CH3), 1.04 (d, J = 7.0 Hz, 3H, CH3), -16.45 (s, 1H, OsH, J satellites (OsH) = 95.22). 13C {1H} NMR ([D2] DCM) δ = 188.57 (d, J (CP) = 8.6 Hz, CO), 161.56 (s, 1C, Py), 153.89 (d, J (CP) = 1.7 Hz, 1C; Py), 136.16 (s, 1C; Py), 125.13 (d, J (CP) = 2.0 Hz, 1C; Py), 121.80 ( d, J (CP) = 1.7 Hz, 1C; Py), 60.62 (d, J (CP) = 2.3 Hz, 1C; CH2), 54.96 (d, J (CP) = 1 , 7 Hz, 1C; CH2), 33.07 (d, J (CP) = 25.9 Hz, 1C; CH), 29.19 (d, J (CP) = 30.3 Hz, 1C; CH) , 26.03 (d, J (CP) = 33.1 Hz, 1C; CH2), 21.04 (d, J (CP) = 3.9 Hz, 1C; CH3), 20.57 (d, J (CP) = 3.4 Hz, 1C; CH3), 19.05 (s, 1C; CH3), 17.51 (d, J (CP) = 4.6 Hz, 1C; CH3). IR (Nujol): VCEO = 1879 (s) Anal. Calculated for C15H26CIN2OOSP: C, 35.53; H, 5.17; N, 5.24, Found: C, 35.35; H, 5.19; N, 5.24, Example 4 - Synthesis of pN- / ner, fac- {OsH (CO) [PyCH2N (CH2) 2P- (/ Pr) 2]} 2

    [0073] A mixture of OsHCI (CO) [PyCH2NH (CH2) 2P (/ Pr) 2] (1.00 g, 1.97 mmol) and KOtBu (243 mg, 2.17 mmol) in 7 mL of THF was stirred for two hours and then the resulting solution was placed in a freezer for one hour. The red reaction mixture was filtered into a 20 ml flask, and 1 ml of THF was used to wash the fried funnel. The solution was diluted with 6 ml of diethyl ether and the compound was crystallized in a freezer at -18 ° C. The bright yellow crystalline product was isolated by filtration and dried under vacuum for 1 h. Yield: 621 mg (67%).
    [0074] 31P NMR ([D2] DCM) δ = 67.73 (s), 51.50 (s). 1H {31P} NMR ([D2] DCM) δ = 8.86 (t, J = 6.7 Hz, 2H, Py), 7.08 (t, J = 7.8 Hz, 1H, Py), 7 , 01 (t, J = 7.6 Hz, 1H, Py), 6.86 - 6.73 (m, 2H, Py), 6.34 (d, J = 8.0 Hz, 1H, Py), 6.24 (d, J = 7.8 Hz, 1H, Py), 5.24 (d, J = 17.8 Hz, 1H, PyCH2), 4.72 (d, J = 19.4 z, 1H , PyCH2), 4.14 (d, J = 17.7 Hz, 1H, NCH2), 3.84 (t, J = 12.9 Hz, 1H, NCH2), 3.80 - 3.68 (m, 1H), 3.56 - 3.33 (m, 3H), 2.75 (hept, J = 14.4, 1H; CH), 2.39 - 2.17 (m, 2H), 2.05 ( hept, J = 5.6, 1H, pCH), 1.99 - 1.87 (m, 1H), 1.83 - 1.62 (m, 1H), 1.32 (overlapping 2d, J = 7, 4 Hz, 3H), 1.28 - 1.16 (m, 1H), 1.09 (d, J = 6.9 Hz, 3H; CH3), 1.05 (d, J = 6.8 Hz, 3H; CH3), 0.95 (d, J = 6.7 Hz, 3H; CH3), 0.89 (d, J = 6.9 Hz, 3H; CH3), 0.73 (d, J = 7 , 0 Hz, 3H; CH3), 0.58 (t, J = 7.3 Hz, 3H), -11.54 (s, 1H; OsH), -14.31 (s, 1H; OsH). 13C {1H} NMR ([D2JDCM) δ = 191.26 (d, J (CP) = 9.0 Hz, 1C; CO), 190.06 (d, J (CP) = 6.7 Hz, 1C; CO), 171.19 (s, 1C; Py), 170.65 (s, 1C; Py), 151.05 (s, 1C; Py), 150.77 (s, 1C; Py), 133.61 (s, 1C; Py), 133.36 (s, 1C; Py), 122.96 (d, J (CP) = 2.0 Hz, 1C; Py), 122.80 (s, 1C; Py) , 117.82 (s, 1C; Py), 75.84 (s, 1C; PyCH2), 74.06 (s, 1C; PyCH2), 70.28 (d, J (CP) = 6.5 Hz, 1C; NCH2), 68.89 (s, 1C; NCH2), 36.42 (d, J (CP) = 28.7 Hz, 1C; CH), 30.73 (d, J (CP) = 21, 3 Hz, 1C; CH), 29.15 (d, J (CP) = 36.4 Hz, 1C; CH), 28.59 (d, J (CP) = 21.8 Hz, 1C; CH), 26.46 (d, J (CP) = 22.2 Hz, 1C; CH2), 26.01 (d, J (CP) = 32.2 Hz, 1C; CH2), 22.32 (d, J ( CP) = 3.6 Hz, 1C; CH3), 20.91 (d, J (CP) = 4.7 Hz, 1C; CH3), 20.17 (d, J (CP) = 2.3 Hz, 1C; CH3), 19.77 (s, 1C; CH3), 19.58 (d, J (CP) = 2.3 Hz, 1C; CH3), 19.09 (s, 1C; CH3), 18, 26 (s, 1C; CH3), 16.77 (d, J (CP) = 7.0 Hz, 1C; CH3). Example 5 - Synthesis of RuHCI (CO) (AsPh3) 3
    [0075] A 250 mL round bottom Schlenk flask was loaded with RuCI3-3H2O (1.26 g, 4.85 mmols), AsPh3 (5.94 g, 19.4 mmols), NEt (/ Pr ) 2 (5.00 g, 38.7 mmols), 2-methoxyethanol (115 ml) and aqueous formaldehyde (40%, 15 ml). The stoppered flask was briefly opened for vacuum and refilled with argon; this procedure was repeated five times. The stirred reaction mixture was heated in an oil bath for 4 hours, maintaining the bath temperature at 125 ° C. The resulting gray suspension was left at room temperature for one hour. The precipitate was filtered, washed with ethanol (3 * 5 ml) and dried under vacuum for two hours to generate an off-white solid. Yield: 3.14 g (66%).
    Complex 3
    [0076] A 25 mL Schlenk flask containing a mixture of RuHCI (CO) (AsPh3) 3 (2.13 g, 2.18 mmols) and PyCH2NH (CH2) 2P (/ Pr) 2 (500 mg, 1, 98 mmol) in 20 mL of toluene was stirred at reflux for one hour at 110 ° C, providing a dark brown solution. After cooling to room temperature, the product was filtered, generating a pale brown powdery solid which was washed with diethyl ether (2x5 ml) and dried under vacuum. Yield: 671 mg (81%).
    [0077] 31P {1H} NMR ([D2] DCM) δ = 94.74 (s). 1H {31P} NMR ([D2] DCM) δ = 8.93 (d, J = 5.3 Hz, 1H; Py), 7.68 (td, J = 7.7, 1.6 Hz, 1H; Py), 7.32 - 7.12 (m, 2H; Py), 4.41 (d, J = 10.2 Hz, 1H; CH2), 4.20 - 3.95 (m, 2H; NH + CH2), 3.57 - 3.40 (m, 1H; CH2), 2.62 (ddd, J = 11.3, 9.3, 3.9 Hz, 1H; CH2), 2.50 (sep, J = 7.1 Hz, 1H; CH), 2.30 (dd, J = 15.0, 3.8 Hz, 1H; CH2), 2.19 (sep, J = 6.9 Hz, 1H; CH ), 1.91 (td, J = 14.6, 5.9 Hz, 1H; CH2), 1.38 (d, J = 7.4 Hz, 3H; CH3), 1.21 (d, J = 7.2 Hz, 3H; CH3), 1.15 - 1.01 (overlapping d, 6H; 2CH3), -14.93 (s, 1H; RuH). 13C {1H} NMR ([D2] DCM) δ = 206.52 (dd due to a31P coupling and residual coupling to the hydroxide, J (CP) = 15.3, 7.3 Hz, 1C; CO), 160, 91 (s, 1C; Py), 153.65 (d, J (CP) = 1.3 Hz, 1C; Py), 136.79 (s, 1C; Py), 124.42 (d, J (CP ) = 2.0 Hz, 1C; Py), 121.57 (d, J (CP) = 1.5 Hz, 1C; Py), 59.80 (s, 1C; PyCH2), 52.98 (s, 1C; NCH2), 32.58 (d, J (CP) = 21.3 Hz, 1C; PCH2), 29.02 (d, J (CP) = 24.9 Hz, 1C; CH), 25.03 (d, J (CP) = 28.5 Hz, 2C; CH), 20.69 (d, J (CP) = 4.2 Hz, 2C; 2xCH3), 19.05 (s, 1C; CH3), 17.61 (d, J (CP) = 5.2 Hz, 1C; CH3). Example 7 - Hydrogenation of esters using complexes 1
    [0078] fBuOK (15 mg, 0.13 mmol) was added to a solution of complex 1 (51 mg, 0.10 mmol) in 10 mL of THF and the mixture was stirred for 3 min. 1 ml of the obtained solution was mixed with methyl benzoate (2.72 g, 20.0 mol) or other desired substrate in 6 ml of THF or toluene. The mixture was then placed in a 75 mL stainless steel reactor (Parr4740) equipped with a magnetic stir bar. The reactor was purged for two pressurization / ventilation cycles with H2 (150 psi and 10 Bar) and then pressurized with H2 (725 psi, Bar 50) and disconnected from the H2 source. The reaction was conducted for 1.5 h at 100 ° C in a preheated oil bath. At the end of the reaction time, the reactor was placed in a cold water bath and was depressurized after cooling to room temperature. The resulting benzyl alcohol was obtained after the evaporation of all volatile compounds (THF, CH3OH) under vacuum. The results are shown in tables 1-4 below. See Table 2 for a complete list of tested substrates. Table 1. Hydrogenation of methyl benzoate catalyzed by complexes 1 - 3, 7 and 9 [a]


    [0079] [a] 20 mmols of PhCOOMe in 7 mL of THF was hydrogenated in a 75 mL Parr pressure vessel, [b] Mole ratio between substrate and metal. [C] With 1 mol% of tBuOK. [d] 120 mmols of PhCOOMe, in a 300 mL container. Table 2. Hydrogenation of esters (AJ) and imines (K, L) that generated the corresponding alcohols and amines, catalyzed by complexes 2, 7 and 9 [a].


    [0080] [a] 20 mmols of substrate in 7 ml of THF was hydrogenated in a 75 ml pressure vessel under p (H2) = 50 Bar. [B] Mole ratio between substrate and metal, [c] 120 mmols of substrate, using a 300 mL container. [d] With 5 mol% of KOMe. [e] With 1 mol% NaOEt. [f] With 10 mol% of KOMe. [g] With 1 mol% of tBuOK. Table 3. Exemplary Substrate - Product Pairs

    Table 4. Hydrogenation of fatty esters catalyzed by complexes
    [a] with tBuOK, 0.5 mol%. [b] A mixture of triglycerides of oleic (ca. 85%), linoleic (ca. 2-3%) and palmitic acids as the main components in our samples. Example 8 - Hydrogenation of methyl benzoate using complex 2
    [0081] 1 ml of a solution containing 4.7 mg / ml of 2 (0.01 mmol [Os]) in THF or toluene was added to a solution of methyl benzoate (2.72 g, 20.0 mmol) in 6 mL of THF or toluene. Subsequent manipulations were performed following the procedure in Example 7. Example 9 - Hydrogenation of olive oil using complex 2
    [0082] 0.6 ml of a solution of 4.7 mg / ml of 2 in toluene (containing 0.006 mmol [Os]) was added to a solution of olive oil (1.86 g, 2.00 mmol) in 6 ml of toluene. All subsequent manipulations were carried out following the procedure in Example 7 using a reaction time of 7 h. The product mixture was evaporated and dried under vacuum for one hour. The additional separation of fatty alcohol from glycerol could be carried out by hexane extraction or by centrifugation and decantation of glycerol fatty alcohol. Example 10 - Hydrogenation of methyl caproate using complex 3
    [0083] 1 ml of a solution of 4.2 mg / ml of 3 (0.01 mmol) in THF or toluene and tBuOK (22.6 mg, 0.2 mmol) were added to a solution of methyl caproate ( 2.94 g, 20.0 mmols) in 6 ml of THF or toluene. All subsequent manipulations were performed following the procedure described in Example 7. Example 11 - Synthesis of NH2 (CH2) 2PPH2
    [0084] In a 500 mL flask, 50.0 g (0.191 mol) of PPha were dissolved in 200 ml of THF and 4.00 g (0.571 mol) of granulated Li was added. The mixture quickly changed color to bright orange, then dark red. The reaction was stirred overnight, and then the generated solution was filtered through a glass frit and a 500 ml flask. The slow addition of 19.3 g (0.166 mol) of 2-chloroethylamine hydrochloride to the filtrate (Caution: Exothermic reaction!) Generated a bright orange solution that was left stirring for another 30 min and then was treated with 3 .00 g H2O. Removal of solvent under vacuum provided a viscous residue. The crude product was washed with 3 x 20 ml of hexane and the remaining white slurry was extracted with 70 ml of toluene and filtered through a short plug (2 cm x 1 cm) of AI2O3. The toluene extract was evaporated using a rotary evaporator and subsequently dried under vacuum to produce 34.69 g (91%) of crude NH2 (CH2) 2PPh2 (83-85%) as a light yellow oil. This product was used without purification in the synthesis of Example 12. Example 12 - Synthesis of PyCH = NCH2CH2PPh2
    [0085] A solution of 2-picolyl aldehyde (23.2 g, 0.216 mol) in 20 ml of THF was slowly added to 60 g (83%, 0.218 mol) of 2-aminoethyl diphenylphosphine in 80 ml of THF and the mixture was stirred for 3 h. Then, 40 ml of hexane was added and the mixture was left in the refrigerator at -18 ° C, which produced an off-white precipitate. The solid was filtered, washed with denatured ethanol (2 x 10 ml) and 40 ml of hexane and then dried under vacuum for two hours. The product was obtained as an off-white solid. Yield 47.2 g (68%).
    [0086] 1H NMR ([D6] Benzene) δ = 8.54 - 8.33 (m, 2H, Py + NCH), 8.09 (dd, J = 7.9, 1.0 Hz, 1H, Py ), 7.54 - 7.32 (m, 4H, Ph), 7.12 - 6.99 (m, 7H, Ph + Py), 6.71 - 6.53 (m, 1H, Py), 3 , 79 - 3.55 (m, 2H, CH2), 2.46 - 2.24 (m, 2H, CH2). 13C NMR ([D6] Benzene) δ = 162.70 (s, 1C, Py), 155.78 (s, 1C, N = C), 149.64 (s, 1C, Py), 139.56 (d , J (CP) = 14.3 Hz, 2C, {ArP} C'pso), 136.05 (s, 1C, Py), 133.30 (d, J (CP) = 19.0 Hz, 4C, {ArP} Corto), 128.87 (s, 2C, {Ar} Cpara), 128.78 (s, 4C, {Ar} Cmeta), 124.53 (s, 1C, Py), 121.04 (s , 1C, Py), 58.45 (d, J (CP) = 20.3 Hz, 1C, NCH2), 30.50 (d, J (CP) = 13.9 Hz, 1C, CH2P). 31P NMR ([D6] Benzene) δ = -18.19 (s). Example 13 - Synthesis of PyCH2NH (CH2) 2PPh2
    [0087] 40 g (0.126 mol) of PyCH = NCH2CH2PPh2 were suspended in 100 ml of methanol in a 250 ml flask, followed by the slow addition of 5.24 g (0.138 mol) of NaBH4 over a period of two hours. After further stirring for 30 min, the mixture was evaporated and the oily residue was extracted with 3 x 30 ml of toluene. The toluene solution was filtered through a short plug of AI2Oa (2 cm x 2 cm), using an additional 2 x 20 mL of toluene to wash the solids. The solvent was removed in vacuo and the product was dried for an additional 2 h to produce 37.2 g (92%) of a pale yellow oil which crystallized after being left over (after 7-10 days) at room temperature.
    [0088] 1H NMR ([D6] Benzene) δ = 8.46 (ddd, J = 4,8,1,7,1,0 Hz, 1H, Py), 7,53 - 7,31 (m, 4H , Ph), 7.12 - 6.91 (m, 6H, Ph), 6.62 (ddd, J = 7.2, 4.8, 1.5 Hz, 1H, Py), 3.79 (s , 2H, CH2), 2.75 (dd, J = 15.2, 8.5 Hz, 2H, CH2), 2.25 - 2.02 (m, 2H, CH2), 1.67 (br. S , 1H, NH). 13C {1H} NMR ([D6] Benzene) δ = 161.06 (s, 1C, Py), 149.48 (s, 1C, Py), 139.74 (d, J (CP) = 14.2 Hz , 2C, {ArP} C'pso), 135.84 (s, 1C, Py), 133.18 (d, J (CP) = 18.8 Hz, 4C, {ArP} Corto), 128.69 ( d, J (CP) = 6.5 Hz, 4C, {ArP} Cmeta), 128.62 (s, 2C, {ArP} Cfor)> 121.94 (s, 1C, Py), 121.61 (s , 1C, Py), 55.39 (s, 1C, CH2N), 46.79 (d, J (CP) = 20.7 Hz, 1C, NCH2), 29.79 (d, J (CP) = 12 , 9 Hz, 1C, CH2P). Example 14 - Synthesis of trans-OsHCI (CO) [PyCH2NH (CH2) 2PPh2]

    [0089] A flask containing a mixture of OsHCI (CO) (AsPh3) 3 (3.00 g, 2.56 mmols) and PyCH2NH (CH2) 2PPh2 (0.818 g, 2.56 mmols) in 30 ml of diglyme was placed in an oil bath preheated to 160 ° C and stirred for 3 hours, providing a dark red solution. After cooling to room temperature, the mixture was diluted with 30 mL of hexane, and the flask was stored for one hour in a freezer at -23 ° C. The precipitated product was filtered, washed with diethyl ether (3x5 ml) and recrystallized from 20 ml of DCM: Et2θ mixture (3: 1). Yield: 779 mg (53%).
    [0090] 1H {31P} NMR ([D2] DCM) δ = 9.04 (d, J = 5.1 Hz, 1H, Py), 7.81 - 7.59 (m, 5H, Ph + Py) , 7.45 - 7.30 (m, 6H, Ph), 7.28 - 7.16 (m, 2H, Py), 4.64 (dd, J = 14.6, 4.4 Hz, 1H, CH2), 4.50 (brt, J = 11.5 Hz, 1H, NH), 3.96 (dd, J = 14.1, 11.7 Hz, 1H, CH2), 3.80 - 3.67 (m, 1H, CH2), 3.09 (dd, J = 14.5, 1.9 Hz, 1H, CH2), 2.74 (dtd, J = 14.7,11.6, 3.3 Hz , 1H, CH2), 2.32 (td, J = 14.6, 5.4 Hz, 1H, CH2), -15.81 (s, 1H, OsH). 13C {1H} NMR ([D2] DCM) δ = 188.19 (dd, J (CP) = 9.2, 5.6 Hz, residual coupling with OsH, 1C, CO), 161.63 (s, 1C , Py), 154.20 (d, J (CP) = 1.5 Hz, 1C, Py), 139.78 (d, J (CP) = 54.6 Hz, 1C, {Ar} Cypso), 136 , 70 (s, 1C, Py), 135.90 (d, J (CP) = 50.4 Hz, 1C, {Ar} Cips0), 133.61 (d, J (CP) = 10.9 Hz, 1C, 2C, {Ar} Corto), 132.69 (d, J (CP) = 10.8 Hz, 2C, {Ar} Corto), 130.50 (d, J (CP) = 2.4 Hz, 1C, {Ar} C for), 130.36 (d, J (CP) = 2.4 Hz, 2C, {Ar} C for), 128.82 (d, J (CP) = 10.4 Hz, 2C, {Ar} Cmeta), 128.66 (d, J (CP) = 10.4 Hz, {Ar} Cmeta), 125.34 (d, J (CP) = 2.0 Hz, Py), 122.02 (d, J (CP) = 1.5 Hz, Py), 60.63 (s, 1C, PyCH2), 53.73 (d, J (CP) = 2.1 Hz, 1C, NCH2), 35, 91 (d, J (CP) = 30.8 Hz, 1C, CH2P). 31P {1H} NMR ([D2] DCM) δ = 29.7 (s). Example 15- Synthesis of trans-RuHCI (CO) [PyCH2NH (CH2) 2PPh2]

    [0091] A 50 mL Schlenk flask containing a mixture of RuHCI (CO) (AsPh3) 3 (5.73 g, 4.68 mmols) and PyCH2NH (CH2) 2PPh2 (1.5 g, 4.68 mmols) in 30 ml of dioxane it was stirred under reflux for 3 hours, providing a dark brown solution. After cooling to room temperature, the mixture was diluted in 5 ml of Et2O and left in a refrigerator at -15 ° C. The crystallized product was filtered, washed with diethyl ether (2x5 ml) and dried in vacuo. Yield: 1.71 g (75%) of a gray solid.
    [0092] 1H {31P} NMR ([D2] DCM) δ = 8.97 (d, J = 5.4 Hz, 1H, Py), 7.95 - 7.55 (m, 5H, Ph + Py) , 7.47 - 7.35 (m, 6H, Ph), 7.33 - 7.26 (m, 1H, Py), 7.22 (d, J = 7.8 Hz, 1H, Py), 4 , 45 (dd, J = 15.3, 4.2 Hz, 2H, PyCH2), 4.09 (dd, J = 15.3, 12.7 Hz, 1H, CH2), 3.71 - 3.51 (br, 1H, NH), 3.00 (dd, J = 14.1, 1.8 Hz, 1H, CH2), 2.75 (dtd, J = 14.3,11.3, 3.1 Hz , 1H, CH2), 2.53 (td, J = 14.4, 5.1 Hz, 1H, CH2), -14.30 (s, 1H, RuH). 13C {1H} NMR ([D2] DCM) δ = 205.80 (d, J (CP) = 17.9 Hz), 160.84 (s, 1C, Py), 153.92 (d, J (CP ) = 1.1 Hz, 1C, Py), 138.73 (d, J (CP) = 49.5 Hz, 1C, {Ar} Cips0), 137.14 (s, 1C, Py), 135.66 (d, J (CP) = 43.7 Hz, 1C, {ArJC ^ 0), 133.46 (d, J (CP) = 11.0 Hz, 2C, {Ar} Corto), 132.62 (d , J (CP) = 11.4 Hz, 2C, {Ar} Corto), 130.44 (d, J (CP) = 2.4 Hz, 1C, {Ar} CPara), 130.34 (d, J (CP) = 2.3 Hz, 1C, {Ar} C for), 128.84 (d, J (CP) = 10.1 Hz, 2C, {Ar} Cmeta), 128.61 (d, J (CP ) = 10.1 Hz, 2C, {Ar} Cmeta), 124.61 (d, J (CP) = 2.2 Hz, 1C, Py), 121.75 (d, J (CP) = 1.6 Hz, 1C, Py), 59.77 (d, J (CP) = 1.5 Hz, 1C, CH2), 51.92 (d, J (CP) = 4.1 Hz, 1C, CH2), 35 , 14 (d, J (CP) = 26.0 Hz, 1C, CH2). Anal. Calculated for C20H2ICIN2ORUP: C, 47.23; H, 6.61; N, 7.34, Found: C, 46.95; H, 6.53; N, 7.15. Example 16 - Typical Procedure for Dehydrogenation of Alcohol Without Acceptor
    [0093] A 50 mL Schlenk flask equipped with a stir bar was loaded with 0.052 mmol of Complexes 2, 3 or 5, 0.5 - 1 mol% of tBuOK (with 3 and 5), and the amount calculated from substrate (1000: 1, substrate to metal ratio) under argon. Then, the flask (attached to and ventilated through an argon support) was placed in an oil bath, where it was heated to a temperature slightly above the boiling point of pure alcohol. Conversion was monitored by 1H NMR spectroscopy using 0.6 mL samples taken from the reaction solutions through the septum stopper using a syringe. Table 5. Results of catalytic dehydrogenation of alcohols without acceptors.
    [a] Using 52 mmol of pure substrate and 1 mol% EtONa for catalyst 7. [b] Mole ratio between substrate and metal, [c] In toluene. [d] With 0.5 mol% of tBuOK. [e] With 1 mol% of tBuOK. [f] Using 0.1 mol of pure substrate, [g] Using 0.2 mol of pure substrate, [h] Reaction was prepared in air using standard anhydrous grade ethanol. Example 17 - Synthesis of PyCH2NH (CH2) 2PtBu2
    [0094] The synthesis of NH2 (CH2) 2PtBu2 was carried out according to a known procedure (6, incorporated herein by reference). A solution of 2-picolyl aldehyde (2.04 g, 19.04 mmols) in 10 ml of THF was added to 2- (di-tert-butylphosphino) ethylamine (3.60 g, 19.04 mmols) in 10 ml of THF. The mixture was stirred for 1 h and then evaporated and dried in vacuo for 1 h. The oily residue was redissolved in 15 ml of toluene and was slowly (over a period of 1 h) treated with a 1.5 M solution of DIBAL in toluene (16.5 ml, 24.75 mmol) (Caution: exothermic reaction! ). The product solution was stirred for 30 min, and then cooled with 1 ml of water (Caution: exothermic reaction!). The resulting suspension was filtered through a short plug (21 cm) of basic alumina and the solids were washed with THF (3x10 ml). The filtrate was evaporated and dried in vacuo for 3 h to generate the product as a yellow oil (3.79 g, 71%).
    [0095] 1H {31P} NMR ([D6] Benzene) δ = 8.49 (d, J = 4.8 Hz, 1H, Py), 7.19-7.15 (m, 1H, Py superimposed with CβDsH ), 7.10 (t, J = 7.1 Hz, 1H, Py), 6.64 (dd, J = 6.3, 5.8 Hz, 1H, Py), 3.96 (s, 2H, PyCH2), 2.87 (t, J = 7.7 Hz, 2H, NCH2), 1.91 (br, 1H, NH) 1.56 (t, J = 7.7 Hz, 2H, CH2P), 1 , 07 (s, 18H, CH3). 13C {1H} NMR ([D6] Benzene) δ = 161.46 (s, 1C, Py), 149.48 (s, 1C, Py), 135.84 (s, 1C, Py), 121.91 ( s, 1C, Py), 121.58 (s, 1C, Py), 55.79 (s, 1C, CH2), 50.78 (d, J (CP) = 34.2 Hz, 1C, CH2), 31.19 (d, J (CP) = 22.1 Hz, 2C, CMe3), 29.82 (d, J (CP) = 14.0 Hz, 6C, CH3), 22.96 (d, J ( CP) = 27.5 Hz, 1C, CH2P). 31P {1H} NMR ([D6] Benzene) δ = 20.47 (s). Example 18 - Synthesis of trans-RuHCI (CO) [PyCH2NH (CH2) 2PtBu2]
    Complex 6
    [0096] A mixture of RuHCI (CO) (AsPh3) 3 (1.93 g, 1.79 mmol) and PyCH2NH (CH2) 2PtBu2 (500 mg, 1.79 mmol) in 10 mL of diglyme was stirred for 3 hours at 140 ° C, in a 50 mL Schlenk flask. After cooling to room temperature, 2 ml of Et2θ were added and the mixture was left to crystallize at -18 ° C. The product was filtered, washed with diethyl ether (2x3 ml) and dried under vacuum for 3 h to generate a gray solid. Yield: 431 mg (54%).
    [0097] 1H {31P} NMR ([D2] DCM) δ = 8.89 (dt, J = 5.4, 0.8 Hz, 1H; Py), 7.66 (td, J = 7.7, 1.6 Hz, 1H; Py), 7.22 (dd, J = 15.5, 7.2 Hz, 2H; Py), 4.68 (br., 1H; NH), 4.45 (dd, J = 15.0, 4.7 Hz, 1H; CH2), 4.00 (dd, J = 14.9, 11.5 Hz, 1H; CH2), 3.61 - 3.44 (m, 1H; CH2), 2.67 (dtd, J = 13.4, 11.6, 4.8 Hz, 1H; CH2), 2.26 (dd, J = 14.7, 4.2 Hz, 1H; CH2) , 2.07 (td, J = 14.2, 6.4 Hz, 1H; CH2), 1.35 (d, J = 5.3 Hz, 18H; CH3), -15.59 (s, 1H; RuH). 13C {1H} NMR ([D2] DCM) δ 206.49 (dd, J (CP) = 15.5, J (CH) = 6.9 Hz residual coupling with OsH, 1C; CO), 160.73 ( s, 1C; Py), 153.59 (s, 1C; Py), 136.74 (s, 1C; Py), 124.37 (d, J (CP) = 1.6 Hz, 1C; Py), 121.33 (s, 1C; Py), 52.51 (s, 1C; CH2), 38.29 (d, J (CP) = 15.0 Hz, 1C; CH2), 37.55 (d, J (CP) = 24.6 Hz, 1C; CMe3), 37.52 (d, J (CP) = 24.6 Hz, 1C; CMe3), 30.93 (d, J (CP) = 4.3 Hz , 3C; CH3), 30.07 (d, J (CP) = 3.2 Hz, 3C; CH3), 28.49 (d, J (CP) = 14.9 Hz, 1C; PCH2). 31P {1H} NMR ([D2] DCM) δ 106.10 (s). Anal. Calculated for CI H3ICIN2OPRU: C, 45.68; H, 6.99; N, 6.27. Found: C, 45.40; H, 6.74; N, 5.92, Example 19 - Trans-RuCl2 (PPh3) synthesis [PyCH2NH (CH2) 2PPh2]
    Complex 7
    [0099] Stirring a mixture of RuCl2 (PPh3) 3 (4.20 g, 4.38 mmols) and PyCH2NH (CH2) 2PPh2 (1.40 g, 4.38 mmols) in 30 ml of toluene (or 1 , 4-dioxane) for 3 hours at 40 C, in a 100 mL Schlenk flask produced a yellow suspension. The product was filtered in air, washed with 10 ml of Et2θ, and dried under vacuum for 21 hours to generate a yellow solid. Yield: 3.1 g (94%).
    [00100] 1H {31P} NMR ([D2] DCM) δ 8.42 (d, J = 5.6 Hz, 1H; Py), 7.77 - 7.53 (m, 3H), 7.53 - 6.91 (m, 29H), 6.85 (t, J = 6.6 Hz, 1H; Py), 5.49 (t, J = 13.0 Hz, 1H; CH2), 5.23 (br , 1H; NH), 4.28 (dd, J = 13.9, 3.5 Hz, 1H; CH2), 3.66 - 3.31 (m, 2H; CH2), 2.91 - 2.57 (m, 2H; CH2), 2.35 (s, 3H; CH3T0I). 13C {1H} NMR ([D2] DCM) δ 163.50 (s, 1C; Py), 156.81 (s, 1C; Py), 139.44 (d, J = 32.2 Hz, 2C; { PPh2} CiPS0), 137.89 (s, 1C; Py), 137.13 (d, J (CP) = 39.3, 3C; {PPhsJC ^ 0), 135.95 - 135.29 (m, 6C ; {PPh3} Corto), 135.11 (d, J (CP) = 8.4 Hz, 2C; {PPh2} Corto), 134.47 (d, J (CP) = 9.1 Hz, 2C; { PPh2} Cut), 129.38 (d, J (CP) = 4.5 Hz, 2C; {PPh2} CPara), 129.38 (s, 3C; {PPh3} Cpara), 128.48 - 127.05 (m, 10C; {PPh2} Cmeta + {PPh3} Cmeta), 122.96 (s, 1C; Py), 121.92 (s, 1C; Py), 67.59 (s, 1,4-dioxane), 57.77 (s, 1C; CH2), 49.09 (s, 1C; CH2), 38.77 (d, J (CP) = 27.4 Hz, 1C; CH2). 31P {1H} NMR ([D2] DCM) δ 49.13 (d, J (PP) = 28.9 Hz, 1P), 47.39 (d, J (PP) = 29.0 Hz, 1P). Anal. Calculated for C38H36Cl2N2P2RU C7H8: C, 63.83; H, 5.24; N, 3.31, Found: C, 63.23; H, 5.22; N, 3.34. Example 20 - Synthesis of trans-OsHCI (CO) [PyCH2NH (CH2) 2PíBu2]
    Complex of 8
    [00102] A mixture of OsHCI (CO) (AsPh3) 3 (1.675 g, 1.43 mmol) and PyCH2NH (CH2) 2PtBu2 (400 mg, 1.43 mmol) in 10 mL of diglyme was stirred for 3 hours at 140 ° C ° C, in a 50 mL Schlenk flask. After cooling to room temperature, 2 ml of Et2Ü were added and the product crystallized after being left at -15 ° C. The yellow solid was filtered, washed with diethyl ether (2x3 mL) and dried in vacuo. Yield: 507 mg (66%).
    [00103] 1H {31P} NMR ([D2] DCM) δ 8.97 (dt, J = 6.3, 1.4 Hz, 1H; Py), 7.67 (td, J = 7.8, 1 , 5 Hz, 1H; Py), 7.27 - 7.05 (m, 2H; Py), 4.65 (dd overlap with br. S, J = 15.8, 4.7 Hz, 2H; CH2 + NH) , 3.88 (dd, J = 15.8, 12.2 Hz, 1H; CH2), 3.69 - 3.43 (m, 1H; CH2), 2.64 (ddd, J = 25.1, 11.4, 4.6 Hz, 1H; CH2), 2.33 (dt, J = 29.2, 14.5 Hz, 1H; CH2), 1.99 (td, J = 14.4, 6, 4 Hz, 1H; CH2), 1.35 (s, 18H; CH3), -17.35 (s, 1H; OsH). 13C {1H} NMR ([D2] DCM) δ 188.49 (dd, J (CP) = 8.3, J (CH) = 4.3 Hz residual coupling with OsH, 1C; CO), 161.44 ( s, 1C; Py), 153.79 (d, J (CP) = 1.7 Hz, 1C; Py), 136.22 (s, 1C; Py), 125.08 (d, J (CP) = 1.8 Hz, 1C; Py), 121.55 (d, J (CP) = 1.6 Hz, 1C; Py), 54.22 (s, 1C; CH2), 39.63 (d, J ( CP) = 20.8 Hz, 1C; CH2), 38.96 (d, J (CP) = 29.1 Hz, 2C; CMe3), 30.90 (d, J (CP) = 3.9 Hz, 3C; CH3), 29.78 (d, J (CP) = 2.6 Hz, 3C; CH3), 29.22 (d, J (CP) = 19.8 Hz, 1C; CH2). 31P {1H} NMR ([D2] DCM) δ 62.79 (s). Anal. Calculated for C17H3iCIN2OPOs: C, 38.16; H, 5.65; N, 5.24, Found: C, 38.04; H, 5.72; N, 4.97. Example 21 - Hydrogenation of imine and ester using complex 7
    [00105] Complex 7 has been further tested in the hydrogenation of compounds with polar bonds C = X. There has been much recent interest in catalytic hydrogenation of esters. While the performance of "state-of-the-art" industrial catalysts is impressive, further improvements are highly desirable to (a) reduce the reaction temperature, preferably as low as 20-40 ° C, and (b) reduce the catalyst load, so preferably less than 0.05 mol%. Guided by these considerations, complex 7 was tested in the hydrogenation of various reference substrates, shown in tables 1-4, above. Note that all reactions shown were performed at 40 ° C.
    [00106] In an argon glove box, the required amount of a 1.9 mg / g solution of 4 in THF was added to the desired amount of base (®uOK, MeOK, or EtOK). The obtained mixture was then mixed with the substrate (0.02 - 0.20 mol) and transferred to a stainless steel Parr reactor (75 ml or 300 ml) equipped with a magnetic stir bar. The reactor was closed, removed from the glove box, tightened and connected to a hydrogen tank. After purging the line, the reactor was pressurized to 725 psi (50 Bar) and disconnected from the 2 H source (with the exception of the reactions carried out in the 300 mL reactor using 0.2 mol of substrate). Then, the reactor was placed in an oil bath preheated to 40 ° C. At the end of the reaction time, the reactor was moved to a cold water bath for 5 min and depressurized.
    [00107] The results of the above hydrogenation experiments demonstrate that an exceptional ethanol dehydrogenation catalyst can also be superior in hydrogenating substrates with C = X polar bonds. Catalyst 7 is particularly successful in reducing alkanoates, generating a volume unprecedented 20,000 turnovers in 16 h for ethyl acetate and 18,800 turnovers in 18 hours for methyl hexanoate, both at 40 ° C. The best turnover number (TON) reported to date for this type of substrate was 7100 in 18 hours at 100 ° C for methyl hexanoate, using a ruthenium dimer {RuH (CO) [N (C2H4PiPr2) 2]} 2 (Spasyuk, D., Smith, S., Gusev, DG Angew.Chem., Int. Ed. 2012, 51,2772-2775). For another comparison, the best Firmenich catalyst, RuCl2 (H2NC2H4PPh2) 2, would theoretically need 27 hours to produce 18600 turnovers for methyl octanoate at 100 ° C, based on the reported TOF = 688 h “1 during a reaction time of 2 , 5 h. (publication of United States patent application No. US 2010-280273). Complex 7 is also a competent imine hydrogenation catalyst, generating a particularly high TON = 50,000 for N-benzylaniline. Example 22 - Synthesis of pN- {RuH (CO) [PyCH2N (CH2) 2P (/ Pr) 2]} 2
    Complex 9
    [00108] A mixture of diethyl ether and THF (2: 1, 15 mL) was added to a mixture of Complex 3 (640 mg, 1.53 mmol) and tBuOK (172 mg, 1.53 mmol) and the resulting solution was stirred for 5 min. During this time the color changed from yellow to dark purple, then to dark green. The product solution was placed in a freezer at -18 degrees Celsius for 15 min and then filtered through a glass frit. The solvent was removed in vacuo to produce 532 mg (91%) of a mixture of two isomers of Complex 4. The main isomer was obtained in a pure form as a bright yellow solid (340 mg, 58%) after recrystallizing the mixture of 5 ml of toluene at 60 ° C.
    [00109] 31P {1H} NMR ([D2] DCM) δ = 93.80 (s), 90.25 (s) .1H {31P} NMR ([D2JDCM) δ = 9.01 (dd, J = 5 .5, 0.8 Hz, 1H; Py), 8.40 (d, J = 5.4 Hz, 1H; Py), 7.15 (td, J = 7.7, 1.6 Hz, 1H; Py), 7.10 (td, J = 7.7, 1.7 Hz, 1H; Py), 6.86 (t, J = 6.5 Hz, 2H; Py), 6.46 (d, J = 7.9 Hz, 1H; Py), 6.27 (d, J = 8.0 Hz, 1H; Py), 4.50 (d, J = 18.0 Hz, 1H; CH2), 4.15 (d, J = 17.9 Hz, 1H; CH2), 4.05 (dd, J = 18.0, 1.6 Hz, 1H, CH2), 3.55 - 3.24 (m, 3H), 3.11 (dd, J = 11.8, 5.3 Hz, 1H; CH2), 2.95 - 2.78 (m, 2H), 2.61 - 2.45 (m, 1H), 2, 37 - 2.17 (m, 2H), 2.03 (dd, J = 13.4, 3.8 Hz, 1H; CH2), 1.91 (hept, J = 7.2 Hz, 1H; CH) , 1.74 (td, J = 14.1, 5.6 Hz, 1H; CH2), 1.53-1.43 (dd superimposed with d, 1H; CH2), 1.44 (d superimposed with dd, J = 7.6 Hz, 3H; CH3), 1.38 (d, J = 2.4 Hz, 3H; CH3), 1.35 (d, J = 1.8 Hz, 3H; CH3), 1, 31 (d, J = 6.9 Hz, 3H; CH3), 1.16 (d, J = 6.8 Hz, 3H; CH3), 1.05 (d, J = 6.9 Hz, 6H; CH3 ), 1.00 (d, J = 6.8 Hz, 3H; CH3), -12.45 (s, 1H; RuH), -13.68 (s, 1H; RuH). 13C {1H} NMR ([D6] Benzene) δ = 209.64 (d, J (CP) = 17.0 Hz, 1C; CO), 207.30 (d, J (CP) = 12.4 Hz, 1C; CO), 169.03 (d, J (CP) = 2.2 Hz, 1C; Py), 168.09 (s, 1C; Py), 155.64 (s, 1C; Py), 151, 26 (s, 1C; Py), 134.92 (s, 1C; Py), 134.51 (s, 1C; Py), 121.37 (d, J (CP) = 2.4 Hz, 1C; Py ), 120.97 (s, 1C; Py), 118.09 (s, 1C; Py), 117.65 (s, 1C; Py), 74.01 (d, J (CP) = 2.6 Hz , 1C; PyCH2), 71.36 (m, 2C; PyCH2 + NCH2), 69.73 (s, 1C; NCH2), 33.66 (d, J (CP) = 22.8 Hz, 1C; CH), 31.68 (d, J (CP) = 11.5 Hz, 1C; CH), 29.39 (d, J (CP) = 4.1 Hz, 1C; CH2), 29.11 (s, 1C; CH2), 26.64 (d, J (CP) = 29.2 Hz, 1C; CH), 25.11 (d, J (CP) = 32.6 Hz, 1C, CH), 21.60 (d , J (CP) = 4.1 Hz, 1C; CH3), 21.47 (d, J (CP) = 5.1 Hz, 1C; CH3), 21.07 (d, J (CP) = 7, 3 Hz, 1C; CH3), 20.94 (d, J (CP) = 5.0 Hz, 1C; CH3), 19.77 (s, 1C; CH3), 19.41 (s, 1C; CH3) , 17.69 (d, J (CP) = 3.2 Hz, 1C; CH3), 17.59 (d, J (CP) = 2.9 Hz, 1C; CH3). Calculated for (CISH25N2RUOP) 2: C, 47.23; H, 6.61; N, 7.34, Found: C, 46.95; H, 6.53; N, 7.15. Example 23 - Determination of the Crystalline Structure of Complex 7
    [00110] The unique crystals of complex 7 were cultivated by slow diffusion of hexanes in a solution saturated in dichloromethane. The data were collected in a Bruker Microstar ™ generator equipped with Helios lenses, Kappa Nonius ™ goniometer and a Platinum-135 detector. Cell refinement and data reduction were done using SAINT ™ (SAINT (1999) Version 6.06; Single Crystal Data Software. Bruker AXS Inc., Madison, Wisconsin, USA). An empirical absorption correction, based on multiple measurements of equivalent reflections, was applied using the SADABS ™ program (Sheldrick, GM (1999). SADABS, Bruker Area Detector Absorption Corrections. Bruker AXS Inc., Madison, Wisconsin, USA) . The space group was confirmed by the XPREP routine of SHELXTL (XPREP (1997) Version 5.10; X-ray data Preparation and Reciprocal space Exploration Program, Bruker AXS Inc., Madison, Wisconsin, USA; SHELXTL (1997) Version 5.10; The Complete Software Package for Single Crystal Structure Determination, Bruker AXS Inc., Madison, Wisconsin, USA). The structure was solved by direct methods and refined by least squares of the complete matrix and Fourier difference techniques with SHELX-97 as a part of the LinXTL toolbox (Sheldrick, GM (1997). SHELXS97, Program for the Solution of Crystal Structures Univ, from Gottingen, Germany; Sheldrick, GM (1997). SHELXL97, Program for the Refinement of Crystal Structures. University of Gottingen, Germany). All non-hydrogen atoms were refined using anisotropic displacement parameters. Hydrogen atoms were defined in calculated and refined positions ∞to riding atoms with a common thermal parameter, except those of the NH fraction and hydrides, which were positioned from residual peaks on the Fourier difference map. Collection parameters and connection distances and angles can be found in tables 5 and 6, respectively. Table 6. Crystal Data Collection and Refinement Parameters for Complex 7
    Table 7. Selected Connection Distances (Â) and Angles (degree) for Complex 7 7


    [00111] All publications, patents and patent applications mentioned in this specification are indicative of the skill level of people skilled in the technique to which this invention belongs and are incorporated by reference in this document to the same extent that each publication, patent or application Individual patent application was specifically and individually indicated to be incorporated by reference.
    [00112] The invention being thus described, it will be evident that it can vary in many aspects. Such variations should not be considered to be a departure from the spirit and scope of the invention, and all such modifications as would be obvious to a person skilled in the art are intended to be included in the scope of the following claims.
    权利要求:
    Claims (19)
    [0001]
    1. Compound, characterized by the fact that it presents the formula (I)
    [0002]
    2. Compound according to claim 1, characterized in that: R3 is H, or C3-8 linear alkyl, C3-8 branched alkyl, C3-8 cyclic alkyl, C3-8 alkenyl, C5-8 aryl, each one of which can be optionally replaced; R4 is H; and R5 is H, a linear C3-8 alkyl, branched C3-8 alkyl, cyclic C3-8 alkyl, C3-8 alkenyl, or C5-8 aryl, each of which may be optionally substituted.
    [0003]
    3. A compound according to claim 1 or 2, characterized by the fact that: (a) R4 and R5 are both H; (b) each Y is C; (c) k is 2, and each X is H; and / or (d) L is a phosphine.
    [0004]
    A compound according to any one of claims 1 to 3, characterized in that the compound of Formula (I) is
    [0005]
    5. Compound according to claim 1, characterized by the fact that: R4 is H; and R5 is linear C3-8 alkyl, branched C3-8 alkyl, cyclic C3-8 alkyl, C3-8 alkenyl, or C5-8- aryl
    [0006]
    6. Compound according to claim 1, characterized by the fact that it presents the formula:
    [0007]
    7. Complex, characterized by the fact that it has Formula (II) or (III) [M (LNN ') Za] (II) Mw [M (LNN') Za] 2 (III) in which: each Z is independently a hydrogen or halogen atom, a C1-6 alkyl group, a hydroxyl, or a C1-6 alkoxy, a nitrosyl (NO), CO, CNR, or PR3, where R is an alkyl or an aryl, preferably PR3 is PMes or PPhs; M is a transition metal, like a group 7 metal, a group 8 metal, like Ru or Os, or a group 9 metal; a is 2 or 3; and each LNN 'is a coordinated linker that is a compound, as defined in any one of claims 1 to 6.
    [0008]
    8. Complex according to claim 7, characterized by the fact that it presents the structure of any one of:
    [0009]
    9. Process for dehydrogenating a substrate, characterized by the fact that it comprises treating a substrate with a catalytic amount of a complex of Formula (II) or (III) [M (LNN ') Za] (II) pw [M (LNN ,) Za] 2 (Hl) in which: each Z is independently a hydrogen or halogen atom, a C1-6 alkyl, a hydroxyl, or a C1-6 alkoxy, a nitrosyl group (NO), CO, CNR, or PR3, where R is an alkyl or an aryl, preferably PR3 is PMes or PPhs; M is a transition metal; a is 2 or 3; and each LNN 'is a coordinated linker that is a compound of Formula (I)
    [0010]
    Process according to claim 9, characterized in that: (i) the substrate comprises at least one alcohol half; or (ii) the substrate is a compound of Formula (IV)
    [0011]
    11. Process according to claim 9, characterized by the fact that the substrate and product pair of the dehydrogenation reaction comprise:
    [0012]
    12. Process for the production of H2, characterized by the fact that it comprises dehydrogenating a substrate by treating the substrate with a catalytic amount of a complex of Formula (II) or (III) [M (LNN ') Za] (II) pN [M (LNN ') Za] 2 (III) in which: each Z is independently a hydrogen or halogen atom, a C1-6 alkyl group, a hydroxyl, or a C1-6 alkoxy, a nitrosyl (NO), CO, CNR, or PR3, where R is an alkyl or an aryl, preferably PR3 is PMes or PPhs; M is a transition metal; a is 2 or 3; and each LNN 'is a coordinated linker that is a compound of Formula (I)
    [0013]
    Process according to claim 12, characterized in that the substrate comprises an amine or thiol alcohol, or in which the substrate is ammonia-borane.
    [0014]
    Process according to claim 12, characterized in that it is for producing ethyl acetate comprising treating ethanol with a catalytic amount of a complex of formula (II) or (III).
    [0015]
    15. Process according to claim 13 or 14, characterized by the fact that the process is free of a hydrogen receptor, and / or the process is a homogeneous process.
    [0016]
    16. Process for hydrogenation of a substrate, characterized by the fact that it comprises treating a substrate with a catalytic amount of a complex of Formula (II) or (III) [M (LNN ') Za] (II) MA / [M ( LNN ') Za] 2 (III) where: each Z is independently a hydrogen or halogen atom, a C1-6 alkyl, a hydroxyl, or a 0-6 alkoxy group, a nitrosyl (NO), CO, CNR, or PR3, where R is an alkyl or an aryl, preferably PR3 is PMes or PPhs; M is a transition metal; a is 2 or 3; and each LNN 'is a coordinated linker that is a compound of Formula (I)
    [0017]
    17. Process according to claim 16, characterized in that the substrate comprises at least one ester, wherein the process optionally proceeds in the presence of molecular hydrogen according to one of the following schemes:
    [0018]
    18. Process according to claim 16, Gf ^ OH + G2 OH characterized by the fact that the pair of substrate and product of the hydrogenation reaction comprises:
    [0019]
    19. Process according to claim 17 or 18, characterized in that it is a solvent-free process.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JP5388570B2|2005-04-05|2014-01-15|フイルメニツヒソシエテアノニム|Hydrogenation of esters using Ru / tetradentate ligand complexes|
    SG182995A1|2005-07-21|2012-08-30|Chevron Phillips Chemical Co|Diimine metal complexes, methods of synthesis, and methods of using in oligomerization and polymerization|
    JP5294303B2|2008-03-31|2013-09-18|国立大学法人神戸大学|Novel N, N, P-tridentate Schiff base ligand compound and asymmetric synthesis using the compound|GB201208589D0|2012-05-16|2012-06-27|Givaudan Sa|Improvements in or relating to organic compounds|
    US10173209B2|2013-03-15|2019-01-08|Dmitri Goussev|Complex catalysts based on amino-phosphine ligands for hydrogenation and dehydrogenation processes|
    EP3012260B1|2013-06-20|2018-11-21|Kuraray Co., Ltd.|Metal complex including tridentate aminodicarbene ligand and hydrogenation reduction method using same|
    GB201401230D0|2014-01-24|2014-03-12|Givaudan Sa|Improvements in or relating to organic compounds|
    CN104804041B|2014-01-26|2018-07-13|中国科学院上海有机化学研究所|NCP ligands, its iridium complex, synthetic method, intermediate and application|
    US10046318B2|2014-12-19|2018-08-14|Dow Silicones Corporation|Ligand components, associated reaction products, activated reaction products, hydrosilylation catalysts and hydrosilylation curable compositions including the ligand components, and associated methods for preparing same|
    EP3310745A1|2015-06-17|2018-04-25|Firmenich SA|Hydrogenation of aldehyde or ketone compounds with fe/tridentate ligands complexes|
    CN104926602A|2015-07-09|2015-09-23|武汉工程大学|Decyl alcohol preparing method by using catalytic hydrogenation of decanone|
    CN106050480B|2016-07-06|2018-09-14|浙江大学|The vehicle-mounted hydrogen-feeding system of liquid organic hydride suitable for hydrogen energy automobile|
    EP3737501A1|2018-01-10|2020-11-18|Basf Se|Use of a ruthenium catalyst comprising a tetradentate ligand for hydrogenation of esters and/or formation of esters and a ruthenium complex comprising said tetradentate ligand|
    JP2021516657A|2018-03-16|2021-07-08|フイルメニツヒ ソシエテ アノニムＦｉｒｍｅｎｉｃｈ Ｓａ|Hydrogenation of carbonyl with quaternary PNNP ligand ruthenium complex|
    CN111153940A|2018-11-08|2020-05-15|中国科学院上海有机化学研究所|PNN tridentate ligand, ruthenium complex, preparation method and application thereof|
    CN109705169B|2019-01-30|2021-05-18|苏州大学|Application of bis-cyclopentadienyl rare earth metal complex in catalyzing amine borane dehydrogenation coupling|
    WO2021001240A1|2019-07-03|2021-01-07|Basf Se|Hydrogenation of esters to alcohols in the presence of a ru-pnn complex|
    CN112570032A|2020-11-17|2021-03-30|广东仁康达材料科技有限公司|Water-soluble hydroformylation catalyst and application thereof|
    法律状态:
    2019-05-14| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-06-04| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2019-08-27| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2020-06-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-11-17| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 20/08/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201161524815P| true| 2011-08-18|2011-08-18|
    US61/524.815|2011-08-18|
    US201261593840P| true| 2012-02-01|2012-02-01|
    US61/593.840|2012-02-01|
    PCT/CA2012/050571|WO2013023307A1|2011-08-18|2012-08-20|Hydrogenation and dehydrogenation catalyst, and methods of making and using the same|
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