WO2015191505A1 - Ligands polydentates et leurs complexes pour la catalyse moléculaire - Google Patents

Ligands polydentates et leurs complexes pour la catalyse moléculaire Download PDF

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WO2015191505A1
WO2015191505A1 PCT/US2015/034793 US2015034793W WO2015191505A1 WO 2015191505 A1 WO2015191505 A1 WO 2015191505A1 US 2015034793 W US2015034793 W US 2015034793W WO 2015191505 A1 WO2015191505 A1 WO 2015191505A1
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ligand
optionally substituted
coordination complex
complex
formula
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PCT/US2015/034793
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Pavel A. DUB
John Cameron GORDON
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Los Alamos National Security, Llc
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Priority to US15/375,055 priority Critical patent/US10550139B2/en

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    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/24—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/25—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
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    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
    • C07D295/125—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/13—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
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    • C07F9/02—Phosphorus compounds
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    • C07F9/5027—Polyphosphines
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms
    • C07F9/655345—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms the sulfur atom being part of a five-membered ring

Definitions

  • the present invention relates generally to polydentate ligands and transition metal complexes of these ligands, some of which are relevant to the area of so-called bifunctional metal-ligand M/NH cooperative molecular catalysis.
  • the catalysts can be used in a wide range of catalytic reactions, including hydrogenation and transfer hydrogenation of unsaturated organic compounds, dehydrogenation of alcohols and boranes, various combinations thereof
  • bifunctional metal-ligand (M/NH) cooperative molecular catalysis in which a non-innocent ligand is proposed to directly participate in substrate activation via an N-H group and/or an act of bond cleavage/formation via N-H proton transfer, respectively.
  • M/NH metal-ligand
  • the bifunctional molecular catalysis based on metal-ligand M/NH cooperation was originally developed for asymmetric hydrogenation and transfer hydrogenation of ketones and imines and is now applicable to variety of chemical transformations with a wide scope and high practicability. They include practical hydrogenation of carboxylic and carbonic acid derivatives, hydrogenation and electroreduction of C0 2 , various acceptorless
  • the present invention is directed to several new classes of ligands, transition metal complexes comprising these ligands, and methods of hydrogenating substrates using these complexes as precatalysts.
  • Some of these ligands show an insensitivity to air, the ability to easily vary structures based on cheap, readily available starting materials (i.e. fine-tuning of ligand conformational, steric and electronic properties) and use simple synthetic procedures and protocols consistent with the concept of green chemistry.
  • Some embodiments of the present invention include ligands having a structure of any one of Formula (I), Formula (II), Formula (III), or Formula (IV):
  • Ri and R 5 are independently at each occurrence optionally substituted Ci_ 6 alkyl, C3-6 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, or optionally substituted arylalkyl; R5 may also be independently optionally substituted alkoxy or optionally substituted aryloxy;
  • R 2 , R3, and R4 are independently at each occurrence H, optionally substituted Ci_ 6 alkyl, C3-6 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, or optionally substituted arylalkyl; and
  • n 1, 2, 3, 4, or 5;
  • n 1, 2, 3, 4, or 5;
  • q is 1, 2, 3, or 4;
  • z is 0 or 1, provided that the ligand of Formula (I) is not:
  • Ri, R 2 , q, and z are as defined for the ligands of Formulae (I) to (IV);
  • n is independently 1 , 2, 3, 4, or 5;
  • n is independently 1 , 2, 3, 4, or 5;
  • z is independently 0 or 1 ;
  • R 7 and R 8 are independently H, optionally substituted Ci_ 6 alkyl, optionally substituted aryl or heteroaryl, or optionally substituted arylalkyl, or together with the carbons to which they are bound form a 5-7 membered cyclic or heterocyclic ring, provided that only one of R 7 and Rs is H. Note that in the structures of Formulae (IX) and (X), when z is 0, the carbonyl group is replaced by a methylene group.
  • Ci_ 6 alkyl of R 2 comprise pendant phosphine or phosphine oxide moieties as described further herein.
  • Still other embodiments include those metal coordination complexes comprising any of the ligands described herein coordinated to at least one transition metal.
  • coordination complexes also described herein as precatalysts, include mononuclear and dinuclear metal complexes. Subset general and specific examples are recited as separate embodiments of this class of embodiments.
  • Further embodiments of the present invention include the use of the inventive catalysts in and methods of affecting the catalytic hydrogenation of unsaturated organic precursors, including the methods of affecting these transformations.
  • Additional embodiments include the use of the inventive catalysts especially, but not exclusively, the bifunctional catalysts in and methods of affecting the catalyses of dehydrogenation of alcohols and boranes, various dehydrogenative couplings, and catalytic stereoselective and achiral C-N and C-C bond-forming reactions, hydration of nitriles, aerobic oxidative transformation of alcohols into ketones and esters.
  • the active catalyst either is the coordination complex as- described or is derived in situ from the presence of the coordination complex under the reaction conditions. While the methods do not depend on the correctness or incorrectness of any suggested catalytic model, it is likely the complex affecting the transformation involves a combination of both of as-described and in sz ' tw-derived complexes.
  • the reaction conditions include the use of strong inorganic base, e.g., alkoxides, as a co-catalyst.
  • FIG. 1 and FIG. 2 show structures of several of the inventive ligands.
  • FIG. 3 A and FIG. 3B show generic structures of several of the inventive ruthenium catalysts.
  • FIG. 4 shows generic structures of several of the inventive iridium catalysts. The various terms are described in the specification.
  • FIG. 5 and FIG. 6 show specific structures prepared during the course of this work.
  • An asterisk (*) indicates that the structure has been determined by X-ray crystallography.
  • FIG. 7 shows selected X-Ray molecular structures for complexes C-2, F-l, D- 1 CH 2 C1 2 , Cu-4, Cu-5 and Cu-8-4MeCN-pentane (50% level of thermal ellipsoids). H-atoms (except NH and OH) are omitted for clarity.
  • FIG. 8 shows a potential mechanism for the conversion of iridium chloride catalysts to a proposed iridium dihydride intermediate generated under hydrogenation conditions.
  • the present invention is directed to several new classes of ligands, catalysts comprising these ligands, and methods of catalyzing a wide range of reactions using these catalysts.
  • compositions e.g., ligands and catalysts
  • processes of making and using said compositions That is, where the disclosure describes or claims a feature or embodiment associated with a composition or a method of making or using a
  • compositions it is appreciated that such a description or claim is intended to extend these features or embodiment to embodiments in each of these contexts (i.e., compositions, methods of making, and methods of using; e.g., features of ligands may be incorporated into the corresponding catalysts, and vice versa).
  • Embodiments described in terms of the phrase “comprising” also provide, as embodiments, those which are independently described in terms of “consisting of and “consisting essentially of.”
  • the basic and novel characteristic(s) of a process is the ability to provide efficient catalysts for the any of the catalytic reactions discussed herein, including reduction of organic substrates and carbon dioxide, oxidation (e.g., acceptorless dehydrogenation of secondary alcohols and aerobic oxidation with oxygen), borylative cyclization, and stereoselective catalytic C-N and C-C bond-forming reactions, catalytic hydration.
  • alkyl refers to a linear, branched, or cyclic saturated hydrocarbon group typically although not necessarily containing 1 to about 24 carbon atoms, preferably 1 to about 12 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl, and the like, as well as cycloalkyl groups such as cyclopentyl, cyclohexyl and the like.
  • lower alkyl intends an alkyl group of 1 to 6 carbon atoms
  • cycloalkyl intends a cyclic alkyl group, typically having 3 to 8, preferably 5 to 7, carbon atoms.
  • substituted alkyl refers to alkyl groups substituted with one or more substituent groups. If not otherwise indicated, the terms “alkyl” and “lower alkyl” include linear, branched, cyclic, unsubstituted, and/or substituted alkyl and lower alkyl groups, respectively.
  • alkoxy intends an optionally substituted alkyl group bound through a single, terminal ether linkage; that is, an “alkoxy” group may be represented as - O-alkyl where alkyl is as defined above.
  • a "lower alkoxy” group intends an alkoxy group containing 1 to 6 carbon atoms.
  • aromatic refers to the ring moieties which satisfy the Hiickel 4n + 2 rule for aromaticity, and includes both aryl (i.e., carbocyclic) and heteroaryl (also called heteroaromatic) structures, including aryl (e.g., phenyl), aralkyl (e.g., benzyl), alkaryl (e.g., tolyl), heteroaryl (e.g., pyridinyl), heteroaralkyl (e.g., pyridinylmethylene), or alk-heteroaryl (e.g., methylpyridinyl) moieties, or oligomeric or polymeric analogs thereof.
  • aryl e.g., phenyl
  • aralkyl e.g., benzyl
  • alkaryl e.g., tolyl
  • heteroaryl e.g., pyridinyl
  • heteroaralkyl e.g., pyri
  • aryl refers to an optionally substituted aromatic substituent or structure containing a single aromatic ring or multiple aromatic rings that are fused together, directly linked, or indirectly linked (such that the different aromatic rings are bound to a common group such as a methylene or ethylene moiety). Unless otherwise modified, the term “aryl” refers to carbocyclic structures. Preferred aryl groups contain 5 to 24 carbon atoms, and particularly preferred aryl groups contain 6 to 14 carbon atoms.
  • aryl groups contain one aromatic ring or two fused or linked aromatic rings, e.g., phenyl, tolyl, naphthyl, biphenyl, diphenylether, diphenylamine, benzophenone, and the like.
  • “Substituted aryl” refers to an aryl moiety substituted with one or more substituent groups
  • heteroatom-containing aryl and “heteroaryl” refer to aryl substituents in which at least one carbon atom is replaced with a heteroatom, as will be described in further detail infra.
  • aryloxy refers to an optionally substituted aryl group bound through a single, terminal ether linkage, wherein “aryl” is as defined above.
  • An “aryloxy” group may be represented as -O-aryl where aryl is as defined above.
  • aralkyl or "arylalkyl” refer to an alkyl group with an optionally substituted aryl substituent, wherein “aryl” and “alkyl” are as defined above.
  • Preferred aralkyl groups contain 6 to 24 carbon atoms, and particularly preferred aralkyl groups contain 6 to 16 carbon atoms.
  • Examples of aralkyl groups include, without limitation, benzyl, 2-phenyl-ethyl, and the like.
  • acyl refers to substituents having the formula -(CO)-alkyl, -(CO)- aryl, or -(CO)-aralkyl
  • acyloxy refers to substituents having the formula -O(CO)- alkyl, -0(CO)-aryl, or -0(CO)-aralkyl, wherein "alkyl,” “aryl, and “aralkyl” are as defined above.
  • catalyst is intended to connote a compound, including a transition metal coordination complex, capable of catalyzing a synthetic reaction, as would be readily understood by a person of ordinary skill in the art.
  • the term is used in the present context of coordination complexes for clarity and convenience only, and is not intended to limit the scope of such complexes to this purpose.
  • coordination complex and catalyst may be used interchangeably, and the person of ordinary skill would be able to understand as such in the context of the description.
  • the term “bifunctional M/NH catalyst” refers to a transition metal complex bearing at least one NH functionality. It is not intended to limit, in any way, the number or types of catalytic reactions to which the catalyst may be effectly applied.
  • cyclic and ring refer to alicyclic or aromatic groups that may or may not be substituted and/or heteroatom-containing, and that may be monocyclic, bicyclic, or polycyclic.
  • alicyclic is used in the conventional sense to refer to an aliphatic cyclic moiety, as opposed to an aromatic cyclic moiety, and may be monocyclic, bicyclic, or polycyclic.
  • acyclic refers to a structure in which the double bond is not contained within a ring structure.
  • halo halide
  • halogen halogen
  • substrate or "organic substrate” are intended to connote both discrete small molecules (sometimes described as “organic compounds”) and oligomers and polymers containing the named functional group or unsaturated bond.
  • ligand is intended to connote a compound capable of coordinating to a metal atom or ion, including transition metal, or a compound which is actually coordinated to such a metal, including transition metal, atom or ion.
  • the term is used in the present context for clarity and convenience only, and is not intended to limit the scope of such compounds to this purpose.
  • reference to compounds and ligands are used interchangeably, and the person of ordinary skill would be able to understand as such in the context of the description.
  • this structure or formula includes any corresponding salt. In the case of amines, this includes amines quaternized, for example, by alkyl or benzyl halides or protic acids.
  • substituted as in “substituted alkyl,” “substituted aryl,” and the like, as alluded to in some of the aforementioned definitions, is meant that in the alkyl, aryl, heteroaryl, or other moiety, at least one hydrogen atom bound to a carbon (or other) atom is replaced with one or more non-hydrogen substituents.
  • substituents include, without limitation, functional groups such as halo (e.g., F, CI, Br, I), hydroxyl, C 1 -C24 alkyl (including C3-8 cycloalkyl), C1-C24 alkoxy, C5-C24 aryl, C5-C24 aryloxy, acyl (including C1-C24
  • alkyl alkylene
  • alkenyl alkenylene
  • alkynyl alkynylene
  • alkoxy aromatic
  • aryl aryloxy
  • alkaryl and “aralkyl” moieties
  • Ligands [0047] Certain specific embodiments of ligands include those having a structure of Formula (I), Formula (II), Formula (III), or Formula (IV):
  • Ri and R 5 are independently at each occurrence optionally substituted Ci_ 6 alkyl, C3-6 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, or optionally substituted arylalkyl; R 5 may also be independently optionally substituted alkoxy or optionally substituted aryloxy;
  • R 2 , R3, and R4 are independently at each occurrence H, optionally substituted Ci_ 6 alkyl, optionally substituted C3-6 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, or optionally substituted arylalkyl; and
  • n 1, 2, 3, 4, or 5;
  • n 1, 2, 3, 4, or 5;
  • q is 1, 2, 3, or 4;
  • R 2 is not H.
  • any compound (ligand or coordination complex / catalyst) known at the time of the invention is to be considered a separate exclusion to the more general descriptions provided here.
  • the coordination complex / catalyst may still be considered within the scope of the invention.
  • these various described compounds, genera, or subgenera may be excluded from the scope of this invention as ligands or discrete compounds, those catalysts, including those of ruthenium and iridium, which comprise these ligands may still be within the scope of the invention. That is, in certain separate embodiments, the descriptions of catalysts include and exclude the specific genera, subgenera, or complexes comprising these ligand compounds. Both are are considered within the scope of the invention.
  • Ci_ 6 alkyl at least with respect to R 2 , includes the substitutents:
  • n is 1, 2, or 3 (preferably 2)
  • z is 0 or 1
  • Ri are phenyl.
  • inventive ligands include those having a structure of Formula (V), Formula (VI), Formula (VII), Formula (VIII), Formula (IX), Formula (X):
  • Ri, R 2 , n, and z are as defined as for the compounds of Formulae (I) to (IV) (note that in the structures of Formulae (IX) and (X), when z is 0, the carbonyl group is replaced by a methylene);
  • R 7 and R 8 are independently H, optionally substituted Ci_ 6 alkyl, optionally substituted aryl or heteroaryl, or optionally substituted arylalkyl, or together with the carbons to which they are bound form a 5-7 membered cyclic or 5-7 membered heterocyclic ring, provided that only one of R 7 and Rg is H.
  • Such heterocyclic rings include those comprising 1 or 2 independent O or N ring atoms.
  • Such exemplary structures include those wherein R 7 and R 8 , together with the carbons to which they are attached, form an optionally substituted cyclopentyl, cyclohexyl, [l,4]dioxanyl, or [l,3]dioxolanyl ring.
  • Such embodiments include structures such as:
  • each Ri is independently phenyl, benzyl, methyl, tert-butyl. See also FIG. 2.
  • Further independent embodiments include those ligands of Formulae (I) to (X), in which Ri is independently methyl, phenyl, or benzyl.
  • Still further independent embodiments include those ligands of Formulae (I) to (X), in which each R 2 is independently H, benzyl, methyl, naphthyl, phenyl, propyl,
  • each R 3 is independently methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert- butyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, benzyl (- Bn), or phenyl (-Ph), or any subset thereof (e.g., H, methyl, phenyl, or benzyl; or H or methyl).
  • the ligands of Formulae (I) to (X) may also independently comprise
  • R 5 is independently lower alkyl, cycloalkyl, or phenyl.
  • E is diarylphosphine or diarylphosphine oxide, dialkylphosphine or dialkylphosphine oxide, alkylarylphosphine or alkylarylphosphine oxide, diarylphosphite or diarylphosphate, dialkylphosphite or
  • dialkylphosphate or alkylarylphosphite or alkylarylphosphate.
  • m and n have been described in terms of 1, 2, 3, 4, or 5, or any subset thereof.
  • m is 1 and n is 1, 2, 3, 4, or 5, or a subset thereof.
  • Other embodiments of Formulae (I) to (X) provide that n is 1 and m is 1, 2, 3, 4, or 5, or a subset thereof.
  • m and n may be independently 2, 3, 4, or 5, or any subset thereof, as applied to any of the compounds of Formulae (I) to (X).
  • the ligands have a structure:
  • the ligands have a structure:
  • R 2 is H or methyl
  • the ligands of Formulae (I) to (XII) may be described in terms of their heteroatom functionality as NNS-type, P(0)NS-type, PNS- type, SNNS-type, SNNP(0)-type, or SNNP-type ligands, depending on the specific nature of E
  • the present invention is also directed to the coordination complexes or catalysts which comprise at least one of the inventive ligands.
  • coordination complex and catalyst may be used interchangeably and are intended to refer to the organometallic entity. While the complexes are useful as catalysts, the use of the term catalyst should not be interpreted to limit the scope of the complexes to this purpose
  • Some of these catalysts comprise catalysts having at least one ligand of Formulae (I) to (X), including NNS-type, P(0)NS-type, PNS-type, SNNS-type, SNNP(0)-type, or SNNP- type ligands, or any described permutations thereof, coordinated to at least one transition metal.
  • such catalysts may be formed by reacting a suitable transition metal precursor with at least one of the ligands described herein. In many cases, this involves the reaction of the corresponding metal chloride or metal olefin complex with the appropriate ligand. While the ligands have been described in terms of certain exclusions, for example, excluding:
  • the catalysts are not necessarily so limited, and in separate embodiments, the catalysts may be free of any individual or combination of excluded ligands or include and or all such ligands or ligand embodiments described herein.
  • transition metal includes any metal of Group 4 to Group 12, including the lanthanides and actinides, preferably one of the Group 6 to Group 11 transition metals.
  • Such transition metals include, but are not limited to Ti, V, Zr, Hf, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, La, Ni, Pd, Pt, Cu, Ag, Au, Zn, and Sm, preferably Cr, Co, Cu, Fe, Mn, Mo, Ni, Os, Pd, Rh, Sm, or W, or any subset combination thereof.
  • the catalysts comprise Fe, Ru, Os, Co, Rh, or Ir, or any subset combination thereof. See also FIG. 6. In other specific embodiments, the catalysts comprise ruthenium or iridium.
  • the catalysts may be described more specifically in terms of their stoichiometries.
  • the ratio of the ligand to transition metal is usually 1 to 1.
  • the catalysts may contain one, two, or more transition metals per molecular entity.
  • the ligands may bridge multiple transition metal centers, or may be monodentate, bidentate, tridentate, or tetradentate with respect to any individual transition metal center.
  • ligands including formally anionic ligands, neutral ligands, or cationic ligands, may be coordinated to the transition metal.
  • exemplary anionic ligands include optionally substituted alkyl, optionally substituted aryl, optionally substituted alkoxy (e.g., methoxy or benzyloxy), optionally substituted aryloxy (e.g., phenoxy), optionally fluorinated carboxylato (e.g., mono-, di-, or trifluoroacetic acid), halo (including fluoro, chloro, bromo, iodo), hydrido, hydroxy, NO, OTf (triflate), OTs (tosylate), phosphate, or BH 4 .
  • At least one of the formally anionic ligands is chloro.
  • Exemplary neutral ligands include C, N, O, P, or S-bonded ligands, such as are known in the art for such transition metal complexes.
  • Such ligands include alkyl or aryl nitriles, alkyl, aryl, or unsubstituted primary, secondary, or tertiary amines, carbonyl, alkyl or aryl ethers (including cyclic ethers, such as tetrahydrofuran), olefins, phosphines, phosphine oxides, phosphites, or alkyl or aryl sulfoxide or other solvent molecules (including lower alcohols and water).
  • Phosphines, phosphine oxides, and phosphites can comprise optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted aryl, or optionally substituted arylalkyl moieties, again as are known in the art.
  • the catalysts may comprise ruthenium having an empirical formula Ru(NNS)XiX 2 L, Ru[P(0)NS]XiX 2 L, Ru(PNS)XiX 2 L, Ru(SNNS)XiX 2 L, Ru[SNNP(0)]XiX 2 L, or Ru(SNNP)XiX 2 L wherein
  • NNS, P(0)NS, PNS, SNNS, SNNP(O), or SNNP is a NNS-type, P(0)NS-type, PNS- type, SNNS-type, SNNP(0)-type, or SNNP-type, respectively;
  • Xi and X 2 are independently formally anionic ligands
  • L is absent or a neutral ligand.
  • L may be absent, for example, when the coordination sphere of the Ru is satisfied without the need for another neutral ligand.
  • the catalysts comprise ruthenium having an empirical formula Ru(NNS)XiX 2 L, wherein NNS, X ls X 2 , and L are as described herein.
  • the catalyst may be independently mononuclear or dinuclear with respect to the ruthenium.
  • R l s R 2 , R3, Xi, X 2 , m, n, z, and E are defined in terms of any of the definitions for these terms provided herein. See also FIG. 3A and 5.
  • Xi and X 2 are independently halo (especially CI), H, OTf, BH 4 ,
  • n and n are independently 1 , 2, 3, 4, or 5, or a subset thereof;
  • z is independently 0 or 1 ;
  • Ri is alkyl, aryl, or arylalkyl (e.g., methyl, phenyl, and benzyl);
  • R 2 is H, alkyl, aryl, or arylalkyl (e.g., methyl, ethyl, propyl, isopropyl, 1 -butyl, 2-butyl, isobutyl, tert-butyl, benzyl, or phenyl); and
  • R 3 is alkyl, aryl, or arylalkyl (for methyl (-CH 3 ), cyclohexyl (-Cy), benzyl (-Bn, -CH 2 Ph), phenyl (-Ph) or napthyl).
  • non-limiting embodiments include those where the structures of the inventive ruthenium complexes may be represented as:
  • Additional specific embodiments include those compounds of Structures (J), (K), or (L) wherein:
  • n and n are independently 1, 2, 3, 4, or 5 or a subset thereof;
  • Ri is alkyl, aryl, or arylalkyl( e.g., methyl, phenyl, and benzyl);
  • P 2 is H, alkyl, aryl, or arylalkyl (e.g., methyl, ethyl, propyl, isopropyl, 1 -butyl, 2-butyl, isobutyl, tert-butyl, benzyl, or phenyl);
  • E is
  • each R 3 is independently methyl, ethyl, propyl, isopropyl, 1 -butyl, 2-butyl, isobutyl, tert- butyl, benzyl (-Bn), and phenyl (-Ph), and
  • q is 1, 2, 3, or 4.
  • Exemplary related structures are shown in FIGs. 3A, 3B, and 5.
  • the catalysts may comprise iridium having an empirical formula Ir(NNS)XiL, Ir[P(0)NS]XiL, Ir(PNS)XiL, Ir(SNNS)XiL, Ir[SNNP(0)]XiL, or
  • NNS, P(0)NS, PNS, SNNS, SNNP(O), or SNNP is a NNS-type, P(0)NS-type, PNS- type, SNNS-type, SNNP(0)-type, or SNNP-type, respectively;
  • Xi is a formally anionic ligand
  • L is a neutral ligand
  • the catalysts comprise iridium having an empirical formula Ir(NNS)X 1 L, wherein NNS, Xi, X 2 , and L are as described herein.
  • R 2 , Xi, m, n, and E are defined in terms of any of the definitions for these terms provided herein.
  • Such structures include, for example:
  • ortho-metallated complexes may be seen as tautomer of the un-metallated complex, and isomer includes geometric isomers, for example, having ligands positioned differently than shown.
  • Xi is halo (e.g., chloro), optionally fluorinated carboxylato (including trifluoroacetato), H, OTf, or BH 4 ,;
  • P 2 is H, alkyl, arylalkyl, or aryl;
  • each P 3 is independently methyl, ethyl, propyl, isopropyl, 1 -butyl, 2-butyl, isobutyl, tert- butyl, benzyl (-Bn), or phenyl (-Ph); and
  • q 1, 2, 3, or 4.
  • some embodiments include those where L is an olefin or a cycloolefm, for example cyclooctene.
  • the transition metal coordination complex may be capable of oxidatively adding H 2 , dihalogen (e.g., Cl 2 , Br 2 , 1 2 ), carboxylate acid (e.g., acetic acid, trifluoroacetic acid, or benzoic acid), hydrogen halide (e.g., HC1, HBr, or HI), alkyl or benzyl halide (e.g., Mel), and dioxygen, as such reactions are known in the art, and the resulting oxidative adducts are considered within the scope of the present invention.
  • dihalogen e.g., Cl 2 , Br 2 , 1 2
  • carboxylate acid e.g., acetic acid, trifluoroacetic acid, or benzoic acid
  • hydrogen halide e.g., HC1, HBr, or HI
  • alkyl or benzyl halide e.g., Mel
  • the present invention is also directed to the use of these coordination complexes or catalysts for the hydrogenation of certain substrates, and the methods of affecting these transformations.
  • These hydrogenations may use dihydrogen or formic acid as the source of the hydrogen in these transformations, and the catalyst may be present in the corresponding reaction mixture either as delivered to the reaction or as derived in situ from the presence of catalyst complex under the reaction conditions.
  • the methods comprise reacting an organic substrate having an unsaturated bond with a source of hydrogen (e.g., dihydrogen, a secondary alcohol, formic acid, or a combination thereof) in the presence of one of the inventive catalysts, under reaction conditions sufficient to hydrogenate the unsaturated bond.
  • a source of hydrogen e.g., dihydrogen, a secondary alcohol, formic acid, or a combination thereof
  • Organic carbonyl or imine double bonds are particularly attractive substrates for these catalysts.
  • the unsaturated bonds may be functionalized or non-functionalized, conjugated or non-conjugated.
  • the catalysts independently catalyze the hydrogenation of ketones and imines, and in the case of those catalysts containing chiral ligands may provide for asymmetric ketone hydrogenation and stereoselective catalytic C-N and C-C bond-forming reactions (e.g, aziridination of alkenes).
  • catalysts provide for the asymmetric transfer hydrogenation of ketones and imines, asymmetric hydrogenation of polar functionalities, asymmetric Michael reaction of 1,3- dicarbonyl compounds with cyclic enones and nitroalkenes, aerobic oxidative kinetic resolution of racemic secondary alcohols and asymmetric hydration of nitriles.
  • Such other catalysts may also be useful for C0 2 , carbonates, ester hydrogenation, and various acceptorless
  • these catalysts may act as precatalysts in C0 2 hydrogenation and electroreduction, ester hydrogenation, ketone transfer hydrogenations, the so lvo lysis of ammonia borane, and the amination of aliphatic alcohols.
  • the methods comprise reacting carbon dioxide, either as carbon dioxide or as a hydration or alcoholic product thereof (e.g., a carbonate) with a source of hydrogen (typically dihydrogen) in the presence of one of the inventive catalysts, under reaction conditions sufficient to hydrogenate the unsaturated bond.
  • a source of hydrogen typically dihydrogen
  • Exemplary operable temperature ranges including those ranges from about 10°C to about 15°C, from about 15°C to about 20°C, from about 20°C to about 25°C, from about 25°C to about 30°C, from about 30°C to about 35°C, from about 35°C to about 40°C, from about 40°C to about 45°C, from about 45°C to about 50°C, from about 50°C to about 55°C, from about 55°C to about 60°C, from about 60°C to about 65°C, from about 65°C to about 70°C, from about 70°C to about 75°C, from about 75°C to about 80°C, from about 80°C to about 85°C, from about 85°C to about 90°C, from about 90°C to about 95°C, from about 95°C to about 100°C, from about 100°C to about 120°C, from about 120°C to about 140°C, from about 140°C to about 160°C, from about 160°C to about 180°C, from
  • Exemplary pressure ranges include those ranges from about 1 bar to about 2 bar, from about 2 bar to about 3 bar, from about 3 bar to about 4 bar, from about 4 bar to about 5 bar, from about 5 bar to about 10 bar, from about 10 bar to about 15 bar, from about 15 bar to about 20 bar, from about 20 bar to about 25 bar, from about 25 bar to about 30 bar, from about 30 bar to about 40 bar, from about 40 bar to about 50 bar, or any combination of these ranges, for example, from about 2 bar to about 50 bar, or from about 5 bar to about 25 bar, where "bar" refers to absolute pressure.
  • these conditions provide sufficient dissolution of hydrogen in most solvents to provide a reaction mixture having convenient turnover rates.
  • a basic co-catalyst appears to be useful in imparting catalytic activity, especially with the bifunctional complexes. Good success has been achieved using alkoxide bases, for example sodium methoxide, though it is envisioned that other alkali metal or alkaline earth metal alkoxides (e.g., including specifically isopropoxides or tert-butoxides) will work as well.
  • alkoxide bases for example sodium methoxide
  • alkali metal or alkaline earth metal alkoxides e.g., including specifically isopropoxides or tert-butoxides
  • the alkoxide activates the transition metal catalyst by displacing other anionic ligands. (see, e.g., FIG. 8).
  • the catalysts appear to be usefully active, especially those based on ruthenium and iridium, and good success has been achieved under these conditions where the substrate to catalyst ratio is in a range of from about 1000:1 to about 50,000: 1, though the invention is not necessarily limited to these conditions.
  • the following listing of embodiments is intended to complement, rather than displace or supersede, the previous descriptions.
  • Embodiment 1 A ligand having a structure of Formula (I), Formula (II), Formula (III), or Formula (IV):
  • Ri and R 5 are independently at each occurrence optionally substituted Ci_ 6 alkyl, C 3 _ 6 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, or optionally substituted arylalkyl; R5 may also be independently optionally substituted alkoxy or optionally substituted aryloxy;
  • R 2 , R 3 , and R4 are independently at each occurrence H, optionally substituted Ci_ 6 alkyl, C 3 _6 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, or optionally substituted arylalkyl; and
  • n 1 , 2, 3, 4, or 5;
  • n 1 , 2, 3, 4, or 5;
  • q is 1 , 2, 3, or 4;
  • R 2 is not H.
  • the one or more of the following compounds may be individually or collectively, in any subset permutation, excluded from the genus of Formula (I):
  • the compounds of Formula (I), where m is independently 1 or 2, n is independently 1 or 2, and Ri is independently phenyl or methyl are excluded from the scope of the present invention.
  • E is independently not phenyl or not methyl.
  • Ri is independently methyl or phenyl
  • E is independently morpholinyl, piperazinyl, and pyrrolidinyl, or dimethylamino in the compounds of Formula (I), then R 2 is not H.
  • Still other aspects of this Embodiment include the salts of these compounds.
  • Ri, R 2 , R 5 , n, and z are as defined in claim 1;
  • R 7 and R 8 are independently H, optionally substituted Ci_ 6 alkyl, optionally substituted aryl or heteroaryl, or optionally substituted arylalkyl, or together with the carbons to which they are bound form a 5-7 membered cyclic or heterocyclic ring, provided that only one of R 7 and Rs is H,
  • Embodiment 3 The ligand of Embodiment 2, wherein R 7 and Rs, together with the carbons to which they are attached, form an optionally substituted cyclopentyl, cyclohexyl, [l,4]dioxanyl, or [l,3]dioxolanyl ring.
  • Embodiment 4 The ligand of any one of Embodiments 1 to 3, wherein Ri is methyl, phenyl, or benzyl.
  • Embodiment 5 The ligand of any one of Embodiments 1 to 4, wherein R 2 is H, methyl, phenyl, or benzyl.
  • Embodiment 6 The ligand of any one of Embodiments 1 to 5, wherein R 2 is H.
  • Embodiment 7 The ligand of any one of Embodiments 1 to 5, wherein R 2 is not H. In certain aspects of this Embodiment, R 2 is methyl.
  • Embodiment 8 The ligand of any one of Embodiments 1 to 7, wherein R 3 is independently methyl, ethyl, propyl, isopropyl, 1 -butyl, 2-butyl, isobutyl, tert-butyl, benzyl (- Bn), or phenyl (-Ph).
  • Embodiment 9 The ligand of any one of Embodiments 1 to 8, where R 5 is optionally substituted phenyl. In certain aspects of this Embodiment, R 5 is unsubstituted phenyl.
  • Embodiment 10 The ligand of any one of Embodiments 1 to 9, wherein E is oxadolidinyl, morpholinyl, imidazolidinyl, N-methyl-imidazolidinyl, piperazinyl, N-methyl- piperazinyl, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, dimethylamino, diethylamino, ethylmethylamino, diarylphosphme or diarylphosphme oxide, dialkylphosphine or dialkylphosphine oxide, alkylarylphosphine or alkylarylphosphine oxide, diarylphosphite or diarylphosphate, dialkylphosphite or dialkylphosphate, or alkylarylphosphite or alkylarylphosphate.
  • E is oxadolidinyl, morpholinyl, imidazolidinyl
  • Embodiment 11 The ligand of any one of Embodiments 1 to 10, wherein m and n are 1.
  • Embodiment 12 The ligand of Embodiment 11, wherein Ri is methyl or benzyl.
  • Embodiment 13 The ligand of any one of Embodiments 1 to 10 or 12, wherein m is 2, 3, 4, or 5 and n is 1.
  • Embodiment 14 The ligand of any one of Embodiments 1 to 10, wherein m and n are independently 2, 3, 4, or 5.
  • Embodiment 15 The ligand of Embodiment 1 or any one of Embodiments 4 to 10, as applied to claim 1, having a structure of Formula (IV).
  • Embodiment 16 The ligand of Embodiment 1 or 15, or any one of Embodiments 4 to 10, as applied to claim 1, having a structure of Formula (IV), wherein n is 2.
  • Embodiment 17 The ligand of Embodiment 1 having a structure of:
  • Embodiment 2 having a structure of:
  • Embodiment 18 A coordination complex comprising a ligand coordinated to at least one transition metal, wherein the ligand is at least one compound of Formulae (I) to (IV) of Embodiment 1 or any one of Embodiments 4 to 17, as applied to Embodiment 1.
  • Embodiment 19 A coordination complex comprising a ligand coordinated to at least one transition metal, wherein the ligand is at least one compound of Formulae (V) to (X) of Embodiment 2, or any one of Embodiments 3 to 17, as applied to Embodiment 2.
  • Embodiment 20 The coordination complex of Embodiment 18 or 19, wherein the transition metal comprises at least one of the Group 4 to Group 12 transition metals, preferably one of the Group 6 to Group 11 transition metals]
  • Embodiment 21 The coordination complex of Embodiment 18 or 19, wherein the transition metal comprises at least one of the Ti, V, Zr, Hf, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, La, Ni, Pd, Pt, Cu, Ag, Au, or Zn, preferably Cr, Co, Cu, Fe, Mn, Mo, Ni, Os, Pd, Rh, Sm, or W.
  • Embodiment 22 The coordination complex of Embodiment 18 or 19, wherein the transition metal is ruthenium or iridium.
  • Embodiment 23 The coordination complex of Embodiment 22, wherein the transition metal is ruthenium, the complex having an empirical formula Ru(NNS)XiX 2 L, Ru[P(0)NS]XiX 2 L, Ru(PNS)XiX 2 L, Ru(SNNS)XiX 2 L, Ru[SNNP(0)]XiX 2 L, or
  • NNS, P(0)NS, PNS, SNNS, SNNP(O), or SNNP is a NNS-type, P(0)NS-type, PNS-type, SNNS-type, SNNP(0)-type, or SNNP-type, respectively;
  • Xi and X 2 are independently formally anionic ligands; and L is absent or a neutral ligand.
  • the complex has an empirical formula of Ru(NNS)XiX 2 L.
  • Embodiment 24 The coordination complex of Embodiment 22, wherein the transition metal is iridium, the complex having an empirical formula Ir(NNS)X 1 L,
  • NNS, P(0)NS, PNS, SNNS, SNNP(O), or SNNP is a NNS-type, P(0)NS-type, PNS-type, SNNS-type, SNNP(0)-type, or SNNP-type, respectively;
  • Xi is a formally anionic ligand
  • the complex has an empirical formula of Ir(NNS)XiL.
  • Embodiment 25 The coordination complex of Embodiment 23 or 24, wherein Xi and X 2 are independently optionally substituted alkyl, optionally substituted aryl, optionally substituted alkoxy, optionally substituted aryloxy, optionally fluorinated carboxylato, halo
  • Xi and X 2 are independently alkoxy, fluorinated carboxylato, halo, hydrido, NO, OTf (triflate), OTs (tosylate) or BH 4 .
  • Embodiment 26 The coordination complex of any one of Embodiments 23 to 25, wherein at least one of Xi and X 2 is chloro.
  • Embodiment 27 The coordination complex of any one of Embodiments 23 to 26, wherein L is absent or a[n alkyl or aryl] nitrile, an [alkyl or aryl] amine, carbonyl, an [alkyl or aryl] ether, a[n alkyl or aryl] phosphine, a[n alkyl or aryl] phosphine oxide, a[n alkyl or aryl] phosphite, a[n alkyl or aryl] phosphate or a[n alkyl or aryl] sulfoxide.
  • L is absent or a[n alkyl or aryl] nitrile, an [alkyl or aryl] amine, carbonyl, an [alkyl or aryl] ether, a[n alkyl or aryl] phosphine, a[n alkyl or aryl] phosphine oxide, a
  • Embodiment 29 The coordination complex of Embodiment 22 or any one of
  • Embodiment 30 The coordination complex of any one of Embodiments 24 to 26, wherein L is an olefin.
  • Embodiment 31 The coordination complex of Embodiment 30, wherein L is cyclooctene.
  • Embodiment 32 An oxidative addition product of the coordination complex of any one of Embodiments 23 to 29.
  • Embodiment 33 The oxidative addition product of Embodiment 32, derived from the addition of H 2 , dihalogen, hydrogen carboxylate, hydrogen halide, alkyl halide to a corresponding precursor coordination complex.
  • the oxidative addition product is derived from the addition of HCl, HBr, HI, Cl 2 , Br 2 , 1 2 , Mel, acetic acid, benzoic acid, and trifluoroacetic acid.
  • Embodiment 34 The coordination complex of Embodiment 18 or 19,
  • FIG. 3 A, FIG. 3B, or FIGs. 4-8 characterized as having a structure of any one of the compounds of FIG. 3 A, FIG. 3B, or FIGs. 4-8, or an isomer or tautomer thereof.
  • Embodiment 37 The method of Embodiment 35 or 36, wherein the unsaturated bond is a carbonyl or imine double bond.
  • Embodiment 39 A method comprising reacting carbon dioxide substrate with dihydrogen in the presence of a catalyst, the catalyst comprising a coordination complex of any one of Embodiments 18 to 34 or derived in situ from the presence of coordination complex of any one of Embodiments 18 to 34, under reaction conditions sufficient to reduce the carbon dioxide by the addition of dihydrogen thereto.
  • Embodiment 40 The method of any one of Embodiments 35 to 39, wherein the conditions sufficient to reduce the carbon dioxide or the unsaturated bond comprise reacting the substrate, the catalyst, and the dihydrogen in the presence of a solvent and a strong base.
  • Embodiment 41 The method of Embodiment 40, wherein the strong base is an alkali metal or alkaline earth metal alkoxide, preferably a methoxide, isopropoxide, or tert- butoxide.
  • the strong base is an alkali metal or alkaline earth metal alkoxide, preferably a methoxide, isopropoxide, or tert- butoxide.
  • Embodiment 42 A method comprising reacting a primary or secondary alcohol (including but not limited to methanol, ethanol, propanol, or isopropanol) in the presence of a catalyst under reaction conditions sufficient to dehydrogenate the primary or secondary alcohol, the catalyst comprising a coordination complex of any one of Embodiments 18 to 34 or derived in situ from the presence of coordination complex of any one of Embodiments 18 to 34 under the reaction conditions.
  • a primary or secondary alcohol including but not limited to methanol, ethanol, propanol, or isopropanol
  • Embodiment 43 A method comprising reacting a primary or secondary alcohol (including but not limited to methanol, ethanol, propanol, or isopropanol) in the presence of a catalyst under reaction conditions sufficient to dehydrogenate the primary or secondary alcohol, the catalyst comprising a coordination complex of any one of Embodiments 18 to 34 or derived in situ from the presence of coordination complex of any one of Embodiments 18 to 34 under the reaction conditions.
  • a primary or secondary alcohol including but not limited to methanol, ethanol, propanol, or isopropanol
  • Embodiment 44 A method comprising reacting an alkene substrate and appropriate reactant (as is known in the art), in the presence of a catalyst, under reaction conditions sufficient to form a cycloalkyl (e.g., cyclopropyl) or aziridine moiety, the catalyst comprising a coordination complex of any one of Embodiments 18 to 34 or derived in situ from the presence of coordination complex of any one of Embodiments 18 to 34 under the reaction conditions.
  • a cycloalkyl e.g., cyclopropyl
  • the catalyst comprising a coordination complex of any one of Embodiments 18 to 34 or derived in situ from the presence of coordination complex of any one of Embodiments 18 to 34 under the reaction conditions.
  • Embodiment 45 A method comprising reacting a nitrile, a borane, or an aliphatic alcohol, in the presence of a catalyst, under reaction conditions sufficient to hydrate the nitrile, solvate the borane, or aminate the alcohol, respectively, the catalyst comprising a coordination complex of any one of Embodiments 18 to 34 or derived in situ from the presence of
  • Example 1 Materials and Methods.
  • Phosphorus tribromide (99%, CAS Number 7789-60-8), 2-(phenylthio)ethanol (99%, CAS Number 699-12-7), 2-(methylthio)ethanol (99%, CAS Number 5271-38-5), ethylene sulfide (98%, CAS Number 420-12-2), trimethylene sulfide (>96.0%, CAS Number 287-27-4), 2-(4-morpholinyl)ethanamine (99%, CAS Number 2038-03-1), 3-morpholinopropylamine (CAS Number 123-00-2), l-(2-aminoethyl)pyrrolidine (98%, CAS Number 7154-73-6), l-(2- aminoethyl)piperazine (99%, CAS Number 140-31-8), 2-chloroethyl methyl sulfide (97%, CAS Number 542-81-4), 2-thiophenecarbaldehyde (98%, CAS Number 98-03-3), (lR,2R)-(-(-(
  • Ts-DENEB T3078, TCI
  • (i?)-RUCY-XylBINAP R0139, TCI
  • Abdur-Rashid's Ir-PNP min 98%, 77-0500 Strem
  • Elemental Analyses were performed by Midwest Microlab, LLC (Indianapolis, IN 46250) under air or under inert atmosphere of nitrogen or argon. All NMR experiments were carried out using a Bruker AV400 MHz spectrometer. 1H and ⁇ C ⁇ FI ⁇ NMR spectra were calibrated by using the residual deuterated solvent signal relative to TMS in ppm ( ⁇ ). 19 F NMR spectra were measured without lock but properly shimmed in methanol and calibrated relative to 2,2,2-trifluoroethanol (product C), with ⁇ set at -77.0 ppm. Magnetic susceptibility
  • Chart 1 illustrates the NNS-type ligands of the general formula
  • Ligands la, lb, lc, Id, le, 2a, 3a, 4a, 4b, and 5a were synthesized according to Scheme 1. The reactions were performed in air inside a fume hood. These ligands are colorless or yellow liquids and were characterized via elemental analysis, 1H and 13 C ⁇ 1 H ⁇ NMR spectroscopy.
  • Example 2.2 Synthesis of ligand lb (3-morpholino- V-(2- (phenylthio)ethyl)propan-l-amine).
  • a solution of 3-morpholinopropylamine (14.6 ml, 0.1 mol) in acetonitrile (200 mL) was prepared.
  • 2-bromoethyl phenyl sulfide (15.1 ml, 0.1 mol) was added to the solution with stirring, followed by anhydrous potassium carbonate (38.9 g, 0.28 mol) also with stirring.
  • the resulting suspension was refluxed for 16 hours, cooled to room temperature, and filtered.
  • Ligand lb was obtained by fractional vacuum distillation on a simple distillation kit containing two theoretical plates. The first collected fraction that boiled at 41 - 46°C corresponds to residual 3-morpholinopropylamine (recovery ⁇ 2.8 ml, transparent liquid).
  • the second collected fraction that boiled at 141 - 156°C corresponds to ligand lb (isolated yield: 15.98 g (57%, based on 2-bromoethyl phenyl sulfide) as a clear almost transparent (slightly yellowish) oil. Elem. Anal: Calc'd for Ci 5 H 2 4N 2 OS (280.43): C, 64.25; H, 8.63; N, 9.99%; Found: C, 64.13; H, 8.88; N, 9.99%.
  • Example 2.3 Synthesis of ligand lc (2-(phenylthio)- V-(2-(pyrrolidin-l- yl)ethyl)ethylamine).
  • a solution of l-(2-aminoethyl)pyrrolidine (4.57 g, 0.04 mol) in acetonitrile (80 mL) was prepared.
  • 2-bromoethyl phenyl sulfide (8.70 g, 0.04 mol) was added to the solution, followed by anhydrous potassium carbonate (15.20 g, 0.11 mol), with stirring.
  • Ligand lc was obtained by fractional vacuum distillation on a simple distillation kit containing two theoretical plates. The first collected fraction boiled at 26 - 28°C and corresponds to residual l-(2- aminoethyl)pyrrolidine (recovery approximately 1 ml). The second collected fraction boiled at 130 - 142 °C and corresponds to ligand lc.
  • Example 2.4 Synthesis of ligand Id ( V , V -dimethyl- V 2 -(2- (phenylthio)ethyl)ethane-l,2-diamine).
  • N,N-dimethylethylenediamine (10.9 ml, 0.1 mol) in acetonitrile (200 mL) were added successively 2-bromoethyl phenyl sulfide (15.08 ml, 0.1 mol) and anhydrous potassium carbonate (38.9 g, 0.28 mol) with stirring.
  • the resulting suspension was refluxed for 16 h, cooled to room temperature, filtered (the filter was washed with acetonitrile 2 x 15 ml) and the solvent was removed by evaporation on rotavap to afford 18.54 g of the viscous yellowish oil (60 °C, 1 h).
  • the desired product was obtained by fractional vacuum distillation on a simple distillation kit containing two theoretical plates. The first collected fraction that boiled at 30 - 33 °C corresponds to N,N-dimethylethylenediamine (recovery ⁇ 2.9 ml). The second collected fraction that boiled at 90 - 1 10 °C corresponds to the desired product.
  • Example 2.5 Synthesis of ligand le (2-(phenylthio)- V-(2-(piperazin-l- yl)ethyl)ethanamine).
  • a solution of l-(2-aminoethyl)piperazine (13.1 ml, 0.1 mol) in acetonitrile (200 mL) was prepared.
  • 2-bromoethyl phenyl sulfide (15.1 ml, 0.1 mol) was added to the solution, followed by anhydrous potassium carbonate (38.9 g, 0.28 mol), with stirring.
  • the resulting suspension was refluxed for 16 h, cooled to room temperature, and filtered.
  • the residue on the filter was washed with acetonitrile, 2 x 15 ml, and the solvent was removed by
  • the second collected fraction boiled at 152 - 173°C and corresponds to a mixture of 2-(4-(2- (phenylthio)ethyl)piperazin- 1 -yl)ethanamine and 2-(phenylthio)-N-(2-(piperazin- 1 - yl)ethyl)ethanamine in a 1 :0.27 ratio (8.36 g, yellow oil) according to 1H NMR Analysis. No further purification was performed.
  • Example 2.6 Synthesis of ligand 2a (2-(methylthio)- V-(2- morpholinoethyl)ethanamine).
  • Method A from MeSCH 2 CH 2 Br.
  • a solution of 2-(4- morpholinyl)ethanamine (5.87 ml, 0.045 mol) in acetonitrile (90 mL) was prepared.
  • 2- bromoethyl methyl sulfide (6.94 g, 0.045 mol) was added to the solution, followed by anhydrous potassium carbonate (17.4 g, 0.13 mol), with stirring.
  • Ligand 2a was obtained by fractional vacuum distillation on a simple distillation kit without theoretical plates. The first collected fraction boiled at 30 - 31°C and presumably corresponds to residual 2-(4-morpholinyl)ethanamine (recovery was
  • Example 2.7 Synthesis of ligand 2a (2-(methylthio)- V-(2- morpholinoethyl)ethanamine).
  • Method B from MeSCH 2 CH 2 Cl. This method was similar to Method A above, but 2-chloroethyl methyl sulfide was used instead of 2-bromoethyl methyl sulfide and the reaction mixture was refluxed for 40 h instead of 16 h.
  • Isolated yield of ligand 2a 3.13 g (34% from 5 g of MeSCH 2 CH 2 Cl). Elem. Anal : Calc'd for C 9 H 20 N 2 OS (204.33): C, 52.90; H, 9.87; N, 13.71%; Found: C, 52.82; H, 10.03; N, 13.50%.
  • Example 2.8 Synthesis of ligand 2d ( V , V -dimethyl- V 2 -(2- (methylthio)ethyl)ethane-l,2-diamine).
  • N,N-dimethylethylenediamine (4.94 ml, 0.045 mol)
  • acetonitrile 90 mL
  • 2-chloroethyl methyl sulfide 5 g, 0.045 mol
  • anhydrous potassium carbonate 17.7 g, 0.13 mol
  • the resulting suspension was refluxed for 40 h, cooled to room temperature, filtered (the filter was washed with acetonitrile 2 x 10 ml) and the solvent was removed by evaporation on a rotavap to afford 5.5 g of the yellowish liquid (60 °C, 1 h).
  • the desired product was obtained by slow fractional vacuum distillation.
  • the first collected fraction that boiled at 25 - 40 °C corresponds to the 1 :2 mixture of starting N ; ,N ; -dimethylethylenediamine and the desired product (recovery ⁇ 1 ml).
  • the second collected fraction that boiled at 40 - 70 °C corresponds to the pure desired product.
  • Example 2.9 Synthesis of ligand 3a (2-morpholino-7V-(2- (benzylthio)ethyl)ethylamine).
  • a solution of 2-morpholinoethylamine (6.56 ml, 0.05 mol) in acetonitrile (100 mL) was prepared.
  • 2-bromoethyl benzyl sulfide (11.56 g, 0.05 mol) was added to the solution, followed by anhydrous potassium carbonate (19.35 g, 0.14 mol), with stirring.
  • the resulting suspension was refluxed for 16 h, cooled to room temperature, and filtered.
  • Ligand 3a was obtained by fractional vacuum distillation on Vigreux column composed of two theoretical plates. The first collected fraction boiled at 34 - 38°C and corresponds to the residual 2-(4-morpholinyl)ethanamine (recovery 1.64 g, approximately 1.7 ml). The second collected fraction boiled at 132 - 158°C and corresponds to ligand 3a.
  • Example 2.10 Synthesis of ligand 4a (3-(benzylthio)- V-(2- morpholinoethyl)propan-l-amine).
  • a solution of 2-(4-morpholinyl)ethanamine (3.4 ml, 0.026 mol) in acetonitrile (50 mL) was prepared.
  • 3-bromopropyl benzyl sulfide (6.36 g, 0.026 mol) was added to the solution, followed by anhydrous potassium carbonate (10 g, 0.072 mol), with stirring.
  • the resulting suspension was refluxed for 16 h, cooled to room temperature, and filtered.
  • Ligand 4a was obtained by fractional vacuum distillation on Vigreux column composed of two theoretical plates. The first collected fraction boiled at 25 - 26°C and corresponds to residual 2-(4-morpholinyl)ethanamine (recovery approximately 0.5 ml).
  • the second collected fraction boiled at 145 - 176 °C and corresponds to the analytically pure ligand 4a (3.57 g, 47%, based on 3-bromopropyl benzyl sulfide). Elem. Anal: Calc'd for Ci 6 H 2 6N 2 OS (294.46): C, 65.26; H, 8.90; N, 9.51%; Found: C, 65.56; H, 9.08; N, 9.75%.
  • Example 2.11 Synthesis of ligand 4b (3-(benzylthio)- V-(3- morpholinopropyl)propan-l-amine). To a solution of 3-morpholinopropylamine (4.64 ml, 0.03 mol) in acetonitrile (65 mL) were added successively 3-bromopropyl benzyl sulfide (7.78 g, 0.03 mol) and anhydrous potassium carbonate (12.40 g, 0.09 mol) with stirring.
  • the resulting suspension was refluxed for 16 h, cooled to room temperature, filtered (the residue on the filter was washed with acetonitrile 2 x 10 ml) and the solvent was removed by evaporation on a rotavap to afford 9.49 g of a yellow solution containing a small amount of a yellow solid (55 °C, 1 h, 40 mbar).
  • the desired product was obtained by fractional vacuum distillation on small Vigreux column composed of two theoretical plates. The first collected fraction that boiled at 33 - 35 °C corresponds to the residual 3-morpholinopropylamine (recovery ⁇ 0.8 ml).
  • Chart 2 illustrates the NNS-type ligands of the formula
  • Example 2.13 Synthesis of ligand 6 (3-(benzylthio)- V-methyl- V-(3- morpholinopropyl)propan-l-amine).
  • a mixture of 4b (1.19 g, 3.858 mmol), formic acid (712 mg, 4 equiv) and 1.75 mL of formaldehyde solution (37 wt. % in H 2 0) was stirred for 2 h at 100 °C in a 50 ml schlenk flask in air.
  • the reaction mixture was cooled, treated with 18 mL of a 20% aqueous solution of NaOH and extracted with 3 x 20 mL of Et 2 0.
  • Example 2.14 Synthesis of ligand 7 (3-(benzylthio)- V -methyl- V 2 , V 2 - dimethyl)propan-l-amine).
  • a solution of A ,A ,N'-trimethyl-l ,3-propanediamine (96% Aldrich, 5 g, 0.043 mol) in acetonitrile (90 mL) was prepared.
  • 3-bromopropyl benzyl sulfide (10.54 g, 0.043 mol) was added to the solution, followed by anhydrous potassium carbonate (16.5 g, 0.12 mol), with stirring.
  • the resulting suspension was refluxed for 16 hours, cooled to room temperature, and filtered.
  • P(0)NS-type and PNS ligands of the type shown in Chart 3 can be or have been prepared and used to make inventive complexes.
  • Ligand 8 was synthesized from diphenylvinylphosphine oxide according to Scheme 4. The reaction was performed in air inside a fume hood. The corresponding phosphine Ligand 8* may be prepared by reduction with a variety of reducing agents, including silanes as shown in Scheme 4 (argon). Such processes are well-documented in literature (see, e.g., Curr. Green Chem., 2014, 1, 182; Org. Lett. 2004, 6, 4675, incorporated by reference herein).
  • Chart 4 illustrates the NNS-type (Ci-symmetry, ligands 10 and 11) and SNNS-Type (C 2 -symmetry, ligands 12 and 12*) chiral Ligands of NNS-type and SNNS-type were synthesized, isolated and subsequently used to make inventive complexes.
  • Ligands 10, 11 and 12 were synthesized according to Scheme 6. The reactions were performed in air inside a fume hood. Ligand 11* may be synthesized by using reduction of 11 with, for example, L1AIH 4 as shown in Scheme 6.
  • Example 4.1 Synthesis of ligand 10 ((/R,2R)-7Vl-(thiophen-2- ylmethyl)cyclohexane-l,2-diamine).
  • a yellow solution of (i?,i?)-DACH (5 g, 43.79 mmol) in 20 ml of H 2 0 was added to 4.91 g (43.79 mmol) of freshly distilled 2-thiophenecarbaldehyde in one portion. The obtained mixture was vigorously stirred for 2 h.
  • the suspension was cooled to room temperature and H 2 0 (20 ml) was added to destroy excess NaBH 4 .
  • To the obtained mixture was added 80 ml of brine and 100 ml of CH 2 C1 2 .
  • the system was shaken, and the organic phase was separated on a separation funnel, washed with brine (3 x 80 ml), dried over anhydrous MgS0 4 , followed by filtration, then concentrated on a rotavap to give 6.88 g of a yellow-red liquid (1 h, 50 °C, 40 mbar).
  • Example 4.2 Synthesis of ligand 11 ((7R,2R)- Vl-(2-(phenylthio)ethyl)- V2- (thiophen-2-ylmethyl)cyclohexane-l,2-diamine).
  • a solution of freshly prepared (phenylsulfanyl)acetaldehyde (668 mg, 4.39 mmol) in 7 ml of MeOH was added to a solution of 9 (922 mg, 4.38 mmol) in 5 ml of MeOH. The obtained mixture was stirred for 20 h to afford an orange (deep-red) solution.
  • NaBH 4 (4 equiv, 663 mg
  • the product was purified by column chromatography (9 > ⁇ 5 cm) on silica gel (Sigma, 230 - 400 mesh, 40 - 63 ⁇ , average pore diameter 60 A, -120 g); eluent: hexane-ethyl acetate 7:3 (4 fractions were eluated) and then CH 2 Cl 2 -MeOH-NH 3 10: 1 :0.5 (this eluent dried over Na 2 S0 4 overnight prior to use; two fractions were collected: desired product and then starting 9 in the end). Yield 861 mg (57%), yellow-dark oil. Elem.
  • Example 4.3 Synthesis of ligand 12. To a stirred solution of (R,R)-OACH (1.53 g, 13.4 mmol, 98%> Aldrich) in 25 ml water containing 2.68 g NaOH (5 equiv, 67 mmol) was added dropwise (phenylthio)acetyl chloride (5 g, 26.8 mmol, 97%> Aldrich).
  • Air-stable ligand 13 was synthesized according to Scheme 7. The reaction was performed in air inside a fume hood. Ligand 13* may be prepared by reduction of 13 with a variety of reducing agents, includin silanes as shown in Scheme 7 (under argon).
  • Example 5.1 Synthesis of ligand 13 ⁇ A mixture of 10 (547 mg. 2.60 mmol) and diphenylvinylphosphine oxide (593 mg, 2.60 mmol) in 3 ml of water was refluxed for 24 h. The organic product was extracted with dichloromethane (3 > ⁇ 5 ml), dried over anhydrous MgSC ⁇ , followed by filtration, then concentrated to give yellow-red oily material (1 120 g, 98% crude yield). The oily material crystallizes as white powder upon passing through chromatography column (silicagel or alumogel) or upon standing to afford white-orange crystals.
  • chromatography column sicagel or alumogel
  • Example 6 Preparation of Catalyst Complexes.
  • Complexes of ruthenium, iridium, manganese, iron, cobalt, nickel or copper comprising the inventive ligands were prepared using the NNS-type, P(0)NS-type, PNS-type, SNNS-type, SNNP(0)-type, and SNNP- type poly dentate ligands and suitable precursors of transition metals under inert atmosphere.
  • Synthesis of ruthenium(II) complexes of the general formula [RuCl 2 (ligand)L] was typically performed by reacting the ligand with a suitable ruthenium precursor such as [RuCl 2 (PPh 3 )3], [RuCl 2 (r
  • a suitable ruthenium precursor such as [RuCl 2 (PPh 3 )3], [RuCl 2 (r
  • Syntheses of iridium(I) or iridium(III) complexes were performed typically by reacting the ligand with a suitable iridium precursor such as [IrCl(r
  • Example 6.1 Synthesis and Characterization of Ruthenium Complexes Using NNS-Type Ligands.
  • Chart 6 illustrates Ruthenium Complexes of NNS-type ligands that were synthesized, isolated and subsequently used as precatalysts in catalytic reactions Chart 6.
  • Schemes 8 and 9 below illustrate several exemplary Ruthenium complexes of NNS-type ligands that were synthesized, isolated and subsequently used as precatalysts in catalytic reactions.
  • transition metal precursors useful for preparing embodiment complexes include, but are not limited to, [RuCl 2 (PPh 3 ) 3 ], [RuCl 2 (r
  • 4 -COD)] flesh, [RuCl 2 (DMSO) 4 ] (DMSO
  • Example 6.1.1 Synthesis of Complex A-l.
  • Method A To [RuCl 2 (PPh 3 ) 3 ] (360 mg, 0.375 mmol) was added a solution of la (100 mg, 0.375 mmol) in 5 ml of CH 2 C1 2 with stirring. The resulting burgundy solution was stirred at room temperature. An analysis of the reaction mixture by 31 P NMR spectroscopy after 1 hour revealed complete conversion of the starting material into the product, indicated by a resonance at ⁇ 40.9 ppm, and the presence of free PPh 3 , ⁇ -5.5 ppm).
  • Example 6.1.3 Synthesis of Complex A-2.
  • Complex A-2 was prepared similarly to complex I Method A (vide supra) with the exception that ligand 2a was used instead of ligand la. After decantation of the mother liquor, the obtained red rhombic crystals were washed with diethyl ether (3 x 10 ml) and vacuum dried overnight.
  • Isolated yield of complex A-2 225 mg (75%) of CssHsgCbNzOPRuS- ICH2CI2 (based on 1H NMR. Elem. Anal: Calc'd for C 33 H 39 Cl 2 N 2 0PRuS- lCH 2 Cl 2 (768.20): C, 51.07; H, 5.17; N, 3.50%.
  • Example 6.1.4 Synthesis of Complex A-3.
  • Complex A-3 was prepared similarly to complex I, following method A ⁇ vide supra) with the exception that ligand 3a was used instead of ligand la. After decantation of the mother liquor, the obtained red crystals were washed with diethyl ether (3 x 10 ml) and vacuum dried overnight. Isolated yield: 209 mg (87%). Elem. Anal: Calc'd for C 2 7H 35 Cl 2 N 2 OPRuS (638.59): C, 50.78; H, 5.52; N, 4.39%.
  • Example 6.1.5 Synthesis of Complex A-6.
  • Complex A-6 was prepared similarly to complex A-l, method A (vide supra) with the exception that ligand 4a was used instead of ligand la. After decantation of the mother liquor, a large (> 1 cm) red crystal was transferred onto a filter frit , washed with diethyl ether (3 x 10 ml), dried under vacuum, broken and vacuum dried overnight. Isolated yield: 238 mg (87%). Elem. Anal: Calc'd for
  • the X-ray structures of these complexes resembled one another other, being 5,5 or 5,6-ruthenacycles in which the three heteroatoms (N, N and S) are located in a single plane.
  • the chlorine atoms are located in trans- orientation to each other, and the PPh 3 moiety is located trans to the NH group.
  • These structures resemble those for known Ru-PNN complexes and for other pincer Ru complexes that include P/N tridentate ligands.
  • Example 6.1.6 Synthesis of Complex J-l.
  • Complex J-l was prepared similarly to complex A-1 following method A with the exception that ligand lb was used instead of ligand la.
  • the air-sensitive mixture was stirred for 2 hours and then concentrated to approximately 40% of the original volume, and then layered with diethyl ether (22 ml) and left for eight days. After decantation of the mother liquor, the obtained red needle crystals were transferred onto a filter frit, washed with diethyl ether (3 x 10 ml) and vacuum dried overnight. Isolated yield: 162 mg (60%). Elem. Anal. : Calc'd for
  • Example 6.1.7 Synthesis of Complex J-2.
  • Complex J-2 was prepared similarly to complex J-1 with the exception that ligand 4b was used instead of ligand lb. After decantation of the mother liquor, the resulting orange solid was transferred to a filter frit, washed with diethyl ether (3 x 10 ml) and vacuum dried overnight. Isolated yield: 134 mg (48%), orange solid. Elem. Anal: Calc'd for C 7 oH 86 Cl 4 N 4 0 2 P 2 Ru 2 S 2 (1485.49): C, 56.60; H, 5.84; N, 3.77%. Found: C, 56.42; H, 5.85; N, 3.73%.
  • J-2 dimeric J-2 is sparingly soluble in CD 2 C1 2 , CDCI 3 , CD 3 OD, acetone- ⁇ and DMF- y.
  • the mother liquor produced red crystals after about 1 week (not quantified).
  • the X-Ray structural analysis identified the product as an unsymmetrical, trichloro-bridged bimetallic complex containing a K 2 [N',5 -bidentate ligand, [Ru ⁇ K 2 (N S)-4b ⁇ (PPh 3 ) ⁇ -Cl) 3 RuCl(PPh 3 ) 2 ] (J-3). This could formally be viewed as the product of an association reaction involving a 16 electron monomer of J-2, (i.e.
  • Example 6.1.8 Synthesis of Complex L-l.
  • Complex L-l was prepared similarly to complex A-1 following method A with the exception that ligand 5 a was used instead of ligand la.
  • Example 6.1.9. Synthesis of Complex B-l The procedure for preparing complex B-l was similar to that for preparing complex A-l, method A, with the exception that ligand lc was used instead of ligand la. After the decantation of the mother liquor, the obtained light pink precipitate was collected on a filter frit, washed with diethyl ether (3 x 10 ml) and vacuum dried overnight. Isolated yield: 218 mg (85%). Elem. Anal.: Calc'd for
  • Example 6.1.10 Synthesis of Complex C-1.
  • Complex C-1 was prepared similarly to complex A-l with the exception that ligand Id was used instead of ligand la.
  • X-ray structures were obtained for both complex B-l and complex C-l.
  • the complexes B-l and C-l are isostructural; their solid state structures are also similar to those of octahedral complexes A-1, A-2, A-3, and A-6.
  • the solution behavior of complexes B-l and C-l was similar to that of complex A-1 in that no detectable amount of a second isomer was observed in solution.
  • Complexes B-l and C-l were tested as pre-catalysts for hydrogenation.
  • Example 6.1.11. Synthesis of Complex A-4 A mixture of [RuCl 2 (COD)] n (309 mg, 1.103 mmol), PCy 3 (309 mg, 1.103 mmol) and la (294 mg, 1.103 mmol) was stirred in toluene (10 ml) at 115 °C for 48 h in a KONTES® pressure tube. After cooling down, the brick colored precipitate was collected on a filter frit, washed with Et 2 0 (3 x 10 ml) and vacuum dried to afford 642 mg of the crude material.
  • Example 6.1.12. Synthesis of Complex K-1 A mixture of [RuCl 2 (COD)] n (155 mg, 0.552 mmol) and la (147 mg, 0.552 mmol) was stirred in toluene (10 ml) at 115 °C for 48 h in Kontes pressure tube. After cooling, a brick-colored precipitate was collected on a filter frit, washed with Et 2 0 (3 x 10 ml) and vacuum dried on the filter. The material was extracted on the filter with 5 x 3 ml CH 2 C1 2 allowing the filtrates to be collected in 5 separate vials. A red solution in each vial was layered with Et 2 0 (20 ml).
  • Example 6.1.14. Synthesis of Complex C-2 A mixture of [RuCl 2 (COD)] n (309 mg, 1.103 mmol), PCy 3 (309 mg, 1.103 mmol) and Id (248 mg, 1.103 mmol) was stirred in toluene (10 ml) at 115 °C for 48 h (in a KONTES® pressure tube). After cooling, the brick colored precipitate was filtered on a filter frit, washed with Et 2 0 (3 x 10 ml) and partially vacuum dried on the filter (vacuum pump). The residue was extracted from the filter frit with dichloromethane (6 > ⁇ 3 ml). The obtained solution was layered with Et 2 0 (100 ml). Red-brown crystals were collected in few days (521 mg, 70%> yield). Elem. Anal: Calcd for
  • Example 6.1.15 Synthesis of Complex C-3. Prepared similarly as Complex C- 2, using ligand 2d. The compound exists in CDC1 3 as a mixture of presumably two diastereomers (79:21 ratio). 31 P ⁇ 1H ⁇ (162 MHz, CDC1 3 , r.t.): ⁇ 28.8 (s, minor, 21%), 29.0 (s, major, 79%). 1H NMR (400 MHz, CDC1 3 , r.t., selected): ⁇ 2.09 (CH 3 , major), 2.59 (CH 3 , major), 2.83 (CH 3 , major), 4.80 (vt, NH minor), 5.09 (vt, NH major).
  • Scheme 10 illustrates Ruthenium Complexes of P(0)NS-type ligands that were synthesized, isolated and subsequently used as precatalysts in catalytic reactions.
  • Example 6.2.1 Synthesis of Complex D-1. To [RuCl 2 (PPh 3 ) 3 ] (420 mg, 0.438 mmol) was added a solution of crude ligand 8 (140 mg, 0.438 mmol) in 6 ml of CH 2 C1 2 with stirring. The resulting burgundy solution was stirred at r.t.
  • Chart 7 illustrates Iridium Complexes of NNS-type ligands that were synthesized, isolated and subsequently used as precatalysts in catalytic reactions.
  • inventive complexes of iridium were prepared by reacting a ligand with a suitable iridium-containing precursor in a suitable solvent.
  • Example 7.1 Synthesis of Complex M-1. In a particular preparation, to
  • Example 7.2 Synthesis of Complex N-2.
  • [IrCl(COE) 2 ] 2 145 mg, 0.162 mmol
  • a solution of ligand 2a 91 mg, 0.324 mmol
  • THF 3 ml
  • the orange-yellow suspension was stirred for 3 h at r.t., and a white precipitate was collected on a frit, washed with diethyl ether (3 x 10 ml) and vacuum dried overnight to afford 100 mg of the final off-white product (61%). Elem.
  • Example 7.5 Synthesis of Complex N-5.
  • To [IrCl(COE) 2 ] 2 145 mg, 0.162 mmol) was added a solution of ligand 6 (104 mg, 0.324 mmol) in toluene (2 ml), then acetonitrile (2 ml) with stirring.
  • the initial orange suspension converted into a red solution upon stirring.
  • the mixture was stirred for 3 h at r.t., concentrated to ⁇ half volume and layered with pentane (22 ml). In 4 days, the mother liquor was decanted from the residue composed of red- yellow crystalline material (bottom) and well-shaped yellow crystals (wall).
  • Example 7.6 Synthesis of Complex N-l . Prepared similarly as N-5, except 7 was used as ligand. Isolated yield: 141 mg (79%>). Elem. Anal: Calcd for Ci 8 H 3 oClIrN 2 OS (508.14): C, 37.82; H, 5.55; N, 5.51%. Found (under nitrogen): C, 37.53; H, 5.33; N, 5.47%. Slowly decomposes in CDC1 3 .
  • IrCl(C 8 Hi 3 )H ⁇ ( i Bu 2 PC 2 H4) 2 NH ⁇ ] was isolated.
  • the [Ir in ClH 2 ⁇ CPr 2 PC 2 H 4 ) 2 NH ⁇ ] (“Ir-PNP") is commercially available and has been reported as (pre)catalyst in ester hydrogenation, ketone transfer hydrogenations, solvolysis of ammonia borane and amination of aliphatic alcohols.
  • transition metal complexes are accessible by reactions of suitable precursors with these inventive ligands.
  • Chart 8 illustrates other complexes of NNS, P(0)NS, SNNS-type ligands that were synthesized, isolated and subsequently used as precatalysts in catalytic reactions.
  • Example 8.2.2 Synthesis of Complex Fe-2. To yellowish FeCl 2 (0.221 mmol, 28 mg) was added a solution of ligand 8 (0.221 mmol, 70 mg) in MeCN (3 ml) under stirring. The obtained solution was stirred for 2 h and layered with diethyl ether (20 ml). The next day a white precipitate was separated, washed with diethyl ether (3 > ⁇ 5 ml) and vacuum dried. Yield: 67 mg (68%), off-white powder. Elem. Anal: Calcd for CnffeCbFeNOPS (446.15): C, 45.77; H, 4.97; N, 3.14%; Found: C, 45.48; H, 4.95; N, 3.06%.
  • Example 8.4 Synthesis of irans-[Ni( 3[N,N',S]-3a)(EtOH)Cl 2 ] (Ni-1).
  • a mixture of NiCl 2 (0.278 mmol, 36 mg) and 3a (0.278 mmol, 79 mg) in anhydrous EtOH (4 ml) was stirred in a KONTES® pressure tube at 90°C. After 44 h, the tube was cooled at -20°C for 1 h, and a greenish precipitate was collected on a frit filter, washed with EtOH (3 x 2 ml), then Et20 (3 x 4 ml) and dried under vacuum overnight. 77 mg of the greenish powder was recovered (61 %). Elem.
  • Example 8.5.3 Synthesis of Complex Cu-3. To a brown CuCl 2 (0.358 mmol, 48 mg) was added a solution of ligand 8 (0.358 mmol, 115 mg) in MeCN (4 ml). A change in color to green was observed ( ⁇ 5 min). The obtained mixture was stirred for 2 h, filtered and the filtrate was layered with diethyl ether (20 ml). The next day, a precipitate was collected, washed with diethyl ether (3 > ⁇ 5 ml) and dried under vacuum overnight. Yield: 122 mg (75%). Elem. Anal.: Calcd for Ci 7 H 22 Cl 2 CuNOPS (453.85): C, 44.99; H, 4.89; N, 3.09%; Found: C, 43.92; H, 4.89; N, 3.03%.
  • Example 8.5.5 Synthesis of Complex Cu-5.
  • a brown suspension of CuCl 2 (40 mg, 0.298 mmol) in MeCN (2 ml) was added a solution of 11 (104 mg, 0.298 mmol) in MeCN (2 ml). Immediate change of the color to green was observed. In ⁇ 1 min, a precipitate started to form under stirring. The obtained suspension was stirred for 2 h, the precipitate was filtered, washed with diethyl ether (3 x 5 ml), pentane (3 x 5 ml) and dried under vacuum overnight. Yield: 111 mg (77%), light-green air- and moisture-stable solid. Elem. Anal.: Calcd for Ci 9 H 26 Cl 2 CuN 2 S 2 (481.00): C, 47.44; H, 5.45; N, 5.82%; Found: C, 46.48; H, 5.33; N, 5.76%.
  • Example 8.5.6.1 Synthesis of Water-Soluble Complex Cu-6.
  • CuS0 4 5H 2 0 500 mg, 2.0 mmol
  • MeOH a solution of ligand 10 (421 mg, 2.0 mmol) in MeOH (10 ml) was added. An immediate change of the color to blue-dark was observed.
  • the mixture was stirred in air for 2 h, the precipitate was filtered, washed with MeOH (3 x 10 ml), diethyl ether (3 x 25 ml) and vacuum dried to afford 660 mg of the product. Elem.
  • Example 8.5.6.2 Synthesis of Complex Cu-7.
  • a suspension of (£)-(+)- ⁇ , - Binaphthyl-2,2'-diyl hydrogenphosphate (97% Aldrich, CAS Number 35193-64-7, 200 mg, 0.574 mmol) in 15 ml of dichloromethane was added a solution of Cu-6 (0.5 equiv, 106 mg, 0.287 mmol) in 10 ml of water.
  • the mixture was stirred in air and NaHC0 3 was added via spatula until two clear phases formed.
  • Brine (5 ml) was added.
  • the blue organic phase was separated.
  • the aqueous phase was washed with dichloromethane (2 x 15 ml).
  • ester methyl trifluoroacetate was chosen as a substrate because homogeneous hydrogenation of MTFA may afford
  • TFAMH trifluoroacetaldehyde methyl hemiacetal
  • TFE 2,2,2-trifluoroethanol
  • TFAMH is an important synthon in the production of various fluorinated chemicals containing CF 3 -groups. TFAMH is also used in medicinal chemistry and in agrochemical research and in materials research. MTFA is typically produced from fluoral and methanol at -78 °C, or via a complicated two-step Swartz-type reaction (including a step with HF in the gas-phase), or by stoichiometric hydrogenation of MTFA using borohydride as a reducing agent. The borohydride reduction is neither environmentally nor economically attractive. A method for catalytically converting MTFA (commercially available at $47 for 25 grams) into TFAMH (commercially available at $50 for 250 milligrams) using molecular hydrogen would provide a less expensive, greener alternative to the known methods.
  • S/C substrate-to-catalyst ratio
  • a mixture of complex (0.005 mmol) and MeONa (135 mg, 2.5 mmol) was stirred in methanol (5 ml) for approximately 1 min (except for J-l and J-2, which were stirred for approximately 15 min to ensure complete dissolution).
  • Runs 4 and 10 provide a comparison of hydrogenation rates of complex N-4 with complex N-5 under otherwise identical reaction conditions. Turnover numbers (TON) for these runs were excellent, exceeding 10,000. Notably, replacement of the NH group of complex XVIII with the N(C3 ⁇ 4) group of complex N-5 resulted in an almost 60% increase in hydrogenation activity. This difference in hydrogenation activity between complex N-4 and complex N-5 was unexpected because it is contrary to what would have been expected based upon the generally accepted behavior and mechanism for bifunctional catalysis in which N-methylated complexes are much less active (if at all) for hydrogenation than their corresponding NH analogs.
  • Example 11 Catalytic Hydrogenation of 2,2,2-trifluoroacetophenone.
  • the catalyst (0.008 mmol: complex N-4: 4.3 mg, complex N-5: 4.4 mg) was dissolved in methanol (20 ml) with stirring. 5 ml of this stock-solution was added to MeONa (5 mol %: 27 mg).
  • the temperature was gently increased to 40 °C and monitored via a 4838 Parr Temperature Controller. Observed stability and accuracy was ⁇ 2 °C.
  • the reactor was moved into a precooled water bath (0 °C) for 5 min and then depressurized.
  • the neat reaction mixture from the liner was then directly analyzed by 1H and 19 F NMR spectroscopy without lock. The balance of material present was unreacted 2,2,2-trifluoroacetophenone ( 19 F).

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  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

La présente invention se rapporte de manière générale à de nouveaux ligands achiraux et chiraux contenant du soufre, de l'azote et du phosphore, appelés ligands polydentates de type NNS, de type P(0)NS, de type PNS, de type SNNS, de type SNNP(0) ou de type SNNP et à des complexes de ces ligands avec des métaux de transition. Les catalyseurs dérivés de ces complexes de ligands et de métaux de transition peuvent être utilisés dans une large gamme de réactions catalytiques, notamment l'hydrogénation et l'hydrogénation par transfert de composés organiques insaturés, la déshydrogénation d'alcools et de boranes, divers couplages avec déshydrogénation et d'autres transformations catalytiques.
PCT/US2015/034793 2014-06-09 2015-06-09 Ligands polydentates et leurs complexes pour la catalyse moléculaire WO2015191505A1 (fr)

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US201562130977P 2015-03-10 2015-03-10
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CN109705168A (zh) * 2019-01-16 2019-05-03 云南师范大学 一种双核镍配位化合物及其制备方法与应用
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CN110227464A (zh) * 2019-06-06 2019-09-13 中南民族大学 一种镍基催化剂的制备方法及其应用于腈类和胺类化合物制备亚胺类化合物的方法
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US10550139B2 (en) 2014-06-09 2020-02-04 Triad National Security, Llc Polydentate ligands and their complexes for molecular catalysis
JP2019516676A (ja) * 2016-05-13 2019-06-20 ディーエスエム アイピー アセッツ ビー．ブイ．Ｄｓｍ Ｉｐ Ａｓｓｅｔｓ Ｂ．Ｖ． アルコールへのエステルの選択的還元
JP2019521954A (ja) * 2016-05-13 2019-08-08 ディーエスエム アイピー アセッツ ビー．ブイ．Ｄｓｍ Ｉｐ Ａｓｓｅｔｓ Ｂ．Ｖ． アルデヒドおよびケトンの選択的還元
CN109195935A (zh) * 2016-05-13 2019-01-11 帝斯曼知识产权资产管理有限公司 醛和酮的选择性还原
JPWO2020032131A1 (ja) * 2018-08-09 2021-08-26 株式会社Adeka 化合物、チオール発生剤、組成物、硬化物及び硬化物の製造方法
JP7422076B2 (ja) 2018-08-09 2024-01-25 株式会社Adeka 化合物、チオール発生剤、組成物、硬化物及び硬化物の製造方法
US11639362B2 (en) 2018-09-04 2023-05-02 Takasago International Corporation Tetradentate diaminodiphosphine ligand and transition metal complex, and method for manufacturing same and application for same
CN112654630A (zh) * 2018-09-04 2021-04-13 高砂香料工业株式会社 四齿二氨基二膦配体、过渡金属络合物及它们的制造方法以及其用途
WO2020050271A1 (fr) * 2018-09-04 2020-03-12 高砂香料工業株式会社 Ligand de diaminodiphosphine tétradentate et complexe de métal de transition, son procédé de préparation et son utilisation
JPWO2020050271A1 (ja) * 2018-09-04 2021-09-16 高砂香料工業株式会社 ４座ジアミノジホスフィン配位子、遷移金属錯体及びそれらの製造方法並びにその用途
JP7369700B2 (ja) 2018-09-04 2023-10-26 高砂香料工業株式会社 ４座ジアミノジホスフィン配位子、遷移金属錯体及びそれらの製造方法並びにその用途
CN112654630B (zh) * 2018-09-04 2024-05-24 高砂香料工业株式会社 四齿二氨基二膦配体、过渡金属络合物及它们的制造方法以及其用途
US12012426B2 (en) 2018-09-04 2024-06-18 Takasago International Corporation Tetradentate diaminodiphosphine ligand and transition metal complex, and method for manufacturing same and application for same
CN109705168B (zh) * 2019-01-16 2021-02-05 云南师范大学 一种双核镍配位化合物及其制备方法与应用
CN109705168A (zh) * 2019-01-16 2019-05-03 云南师范大学 一种双核镍配位化合物及其制备方法与应用
US11370736B2 (en) 2019-04-01 2022-06-28 Triad National Security, Llc Synthesis of fluoro hemiacetals via transition metal-catalyzed fluoro ester and carboxamide hydrogenation
CN110227464A (zh) * 2019-06-06 2019-09-13 中南民族大学 一种镍基催化剂的制备方法及其应用于腈类和胺类化合物制备亚胺类化合物的方法

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