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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/20—General preparatory processes
  • C08G64/32—General preparatory processes using carbon dioxide
  • C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
  • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/22—Organic complexes
  • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
  • B01J31/2208—Oxygen, e.g. acetylacetonates
  • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
• • C—CHEMISTRY; METALLURGY
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  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
  • C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
  • C07F15/06—Cobalt compounds
  • C07F15/065—Cobalt compounds without a metal-carbon linkage
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  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
  • C07F5/06—Aluminium compounds
  • C07F5/069—Aluminium compounds without C-aluminium linkages
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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
  • B01J2531/0213—Complexes without C-metal linkages
  • B01J2531/0216—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
  • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
  • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
  • B01J2531/0252—Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
  • B01J2531/31—Aluminium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
  • B01J2531/62—Chromium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
  • B01J2531/84—Metals of the iron group
  • B01J2531/845—Cobalt

Definitions

• Catalysts capable of effecting the copolymerization of epoxides and carbon dioxide to form aliphatic polycarbonates have been known in the art since the 1960s.
• the early catalysts were based on heterogeneous zinc compounds and suffered from low reactivity, a lack of selectivity for polymer formation vs. cyclic carbonate formation, and a tendency to produce polycarbonates contaminated with ether linkages.
• the present invention provides, among other things, metal complexes having more than one metal center and comprising a tethered activating moiety.
• 2008376-0144 (NOV-029-PCT) invention also provides methods of using such multi-metal complexes.
• provided multi-metal complexes have activity in the copolymerization of carbon dioxide and epoxides.
• the present invention provides a multi-metal complex having an activating species with co-catalytic activity tethered to a ligand complex that is coordinated to at least one metal center of a multi-metal complex.
• the present invention provides metal complexes and methods for using the same in the copolymerization of carbon dioxide and epoxides.
• provided metal complexes have a structure:
• M 1 is a first metal atom
• M 2 is a second metal atom
• ⁇ (Z)TM represents one or more activating moieties attached to the multidentate ligand system, where— ⁇ > ⁇ is a linker moiety covalently coupled to the ligand system, each Z is an activating functional group; and m is an integer from 1 to 4 representing the number of Z groups present on an individual linker moiety.
• the present disclosure encompasses methods for the copolymerization of epoxides and carbon dioxide, such methods comprising contacting one or more epoxides with a metal complex described above in the presence of carbon dioxide.
• the present disclosure encompasses methods for the formation of cyclic carbonates from epoxides and carbon dioxide, such methods
• 2008376-0144 (NOV-029-PCT) comprising contacting one or more epoxides with a metal complex described above in the presence of carbon dioxide.
• the present disclosure encompasses methods for the formation of polyethers, such methods comprising contacting one or more epoxides with a multi-metal complex described above.
• Certain compounds of the present invention can comprise one or more
• inventive compounds and compositions thereof may be in the form of an individual enantiomer, diastereomer or geometric isomer, or may be in the form of a mixture of stereoisomers.
• the compounds of the invention are enantiopure compounds.
• mixtures of enantiomers or diastereomers are provided.
• certain compounds, as described herein may have one or more double bonds that can exist as either a Z or E isomer, unless otherwise indicated.
• the invention additionally encompasses the compounds as individual isomers substantially free of other isomers and alternatively, as mixtures of various isomers, e.g., racemic
• compositions comprising one or more compounds.
• isomers includes any and all geometric isomers and stereoisomers.
• “isomers” include cis- and trans-isomers, E- and Z- isomers, R- and S-enantiomers, diastereomers, (D)-isomers, (L)-isomers, racemic mixtures thereof, and other mixtures thereof, as falling within the scope of the invention.
• a compound may, in some embodiments, be provided substantially free of one or more corresponding stereoisomers, and may also be referred to as "stereochemically enriched.”
• a particular enantiomer may, in some embodiments be provided substantially free of the opposite enantiomer, and may also be referred to as "optically enriched.”
• “Optically enriched,” as used herein, means that the compound is made up of a significantly greater proportion of one enantiomer. In certain embodiments the compound is made up of at least about 90% by weight of an enantiomer. In some embodiments the compound is made up of at least about 95%, 97%, 98%, 99%, 99.5%, 99.7%, 99.8%, or 99.9% by weight of an enantiomer.
• the enantiomeric excess of provided compounds is at least about 90%, 95%, 97%, 98%, 99%, 99.5%, 99.7%, 99.8%, or 99.9%.
• enantiomers may be isolated from racemic mixtures by any method known to those skilled in the art, including chiral high pressure liquid chromatography (HPLC) and the formation and crystallization of chiral salts or prepared by asymmetric syntheses. See, for example, Jacques, et al,
• halo and "halogen” as used herein refer to an atom selected from fluorine (fluoro, -F), chlorine (chloro, -CI), bromine (bromo, -Br), and iodine (iodo, -I).
• aliphatic or "aliphatic group”, as used herein, denotes a hydrocarbon moiety that may be straight-chain (i.e., unbranched), branched, or cyclic (including fused, bridging, and spiro-fused polycyclic) and may be completely saturated or may contain
• aliphatic groups contain 1-30 carbon atoms. In certain embodiments, aliphatic groups contain 1-12 carbon atoms. In certain embodiments, aliphatic groups contain 1-8 carbon atoms. In certain embodiments, aliphatic groups contain 1-6 carbon atoms. In some embodiments, aliphatic groups contain 1-5 carbon atoms, in some embodiments, aliphatic groups contain 1-4 carbon atoms, in yet other embodiments aliphatic groups contain 1-3 carbon atoms, and in yet other embodiments aliphatic groups contain 1-2 carbon atoms.
• Suitable aliphatic groups include, but are not limited to, linear or branched, alkyl, alkenyl, and alkynyl groups, and hybrids thereof such as (cycloalkyl)alkyl, (cycloalkenyl)alkyl or (cycloalkyl)alkenyl.
• the term aliphatic group encompasses aliphatic groups wherein one or more hydrogen atoms are replaced with a halogen atom.
• the term aliphatic group encompasses chlorinated or fluorinated aliphatic groups including perfluorinated compounds.
• epoxide refers to a substituted or unsubstituted oxirane.
• substituted oxiranes include monosubstituted oxiranes, disubstituted oxiranes, trisubstituted oxiranes, and tetrasubstituted oxiranes.
• Such epoxides may be further optionally substituted as defined herein.
• epoxides comprise a single oxirane moiety.
• epoxides comprise two or more oxirane moieties.
• polymer refers to a molecule of high relative molecular mass, the structure of which comprises the multiple repetition of units derived, actually or conceptually, from molecules of low relative molecular mass.
• a polymer is comprised of only one monomer species (e.g., polyethylene oxide).
• a polymer of the present invention is a copolymer, terpolymer, heteropolymer, block copolymer, or tapered heteropolymer of one or more epoxides.
• cycloaliphatic used alone or as part of a larger moiety, refer to a saturated or partially unsaturated cyclic aliphatic monocyclic
• cycloalkyl has 3-6 carbons.
• cycloaliphatic also include aliphatic rings that are fused to one or more aromatic or nonaromatic rings, such as decahydronaphthyl or tetrahydronaphthyl, where the radical or point of attachment is on the aliphatic ring.
• a carbocyclic groups is bicyclic.
• a carbocyclic group is tricyclic.
• a carbocyclic group is polycyclic.
• the term "3- to 8-membered carbocycle” refers to a 3- to 8-membered saturated or partially unsaturated monocyclic carbocyclic ring
• alkyl refers to saturated, straight- or branched-chain hydrocarbon radicals derived by removal of a single hydrogen atom from an aliphatic moiety. Unless otherwise specified, alkyl groups contain 1-12 carbon atoms. In certain embodiments, alkyl groups contain 1-8 carbon atoms. In certain embodiments, alkyl groups contain 1-6 carbon atoms. In some embodiments, alkyl groups contain 1-5 carbon atoms, in some embodiments, alkyl groups contain 1-4 carbon atoms, in yet other embodiments alkyl groups contain 1-3 carbon atoms, and in yet other embodiments alkyl groups contain 1-2 carbon atoms.
• alkyl radicals include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec -butyl, sec-pentyl, iso-pentyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, sec-hexyl, n-heptyl, n-octyl, n-decyl, n-undecyl, dodecyl, and the like.
• alkenyl denotes a monovalent group derived by the removal of a single hydrogen atom from a straight- or branched-chain aliphatic moiety having at least one carbon-carbon double bond. Unless otherwise specified, alkenyl groups contain 2-12 carbon atoms. In certain embodiments, alkenyl groups contain 2-8 carbon atoms. In certain embodiments, alkenyl groups contain 2-6 carbon atoms. In some embodiments, alkenyl groups contain 2-5 carbon atoms, in some embodiments, alkenyl groups contain 2-4 carbon atoms, in yet other embodiments alkenyl groups contain 2-3 carbon atoms, and in yet other embodiments alkenyl groups contain 2 carbon
• Alkenyl groups include, for example, ethenyl, propenyl, allyl, 1,3-butadienyl, butenyl, l-methyl-2-buten-l-yl, allyl, 1,3-butadienyl, allenyl, and the like.
• alkynyl refers to a monovalent group derived by the removal of a single hydrogen atom from a straight- or branched-chain aliphatic moiety having at least one carbon-carbon triple bond. Unless otherwise specified, alkynyl groups contain 2-12 carbon atoms. In certain embodiments, alkynyl groups contain 2-8 carbon atoms. In certain embodiments, alkynyl groups contain 2-6 carbon atoms.
• alkynyl groups contain 2-5 carbon atoms, in some embodiments, alkynyl groups contain 2-4 carbon atoms, in yet other embodiments alkynyl groups contain 2-3 carbon atoms, and in yet other embodiments alkynyl groups contain 2 carbon atoms.
• Representative alkynyl groups include, but are not limited to, ethynyl,
• Carbocycle and "carbocyclic ring” as used herein, refer to monocyclic and polycyclic moieties wherein the rings contain only carbon atoms. Unless otherwise specified, carbocycles may be saturated, partially unsaturated or aromatic, and contain 3 to 20 carbon atoms.
• Representative carbocyles include cyclopropane, cyclobutane, cyclopentane, cyclohexane, bicyclo[2,2, l]heptane, norbornene, phenyl, cyclohexene, naphthalene, and spiro[4.5]decane, to name but a few.
• aryl used alone or as part of a larger moiety as in “aralkyl”, “aralkoxy”, or “aryloxyalkyl”, refers to monocyclic and polycyclic ring systems having a total of six to 20 ring members, wherein at least one ring in the system is aromatic and wherein each ring in the system contains three to twelve ring members.
• aryl may be used interchangeably with the term “aryl ring”.
• aryl refers to an aromatic ring system which includes, but is not limited to, phenyl, biphenyl, naphthyl, anthracyl and the like, which may bear one or more substituents.
• aryl is a group in which an aromatic ring is fused to one or more additional rings, such as benzofuranyl, indanyl, phthalimidyl, naphthimidyl, phenantriidinyl, or tetrahydronaphthyl, and the like.
• the term “8- to 14-membered aryl” refers to an 8- to 14-membered polycyclic aryl ring.
• heteroaliphatic refers to aliphatic groups wherein one or more carbon atoms are independently replaced by one or more atoms selected from the group consisting of oxygen, sulfur, nitrogen, phosphorus, or boron.
• one to six carbon atoms are independently replaced by one or more of oxygen, sulfur, nitrogen, or phosphorus.
• Heteroaliphatic groups may be substituted or unsubstituted, branched or unbranched, cyclic or acyclic, and include saturated, unsaturated or partially unsaturated groups.
• heteroaryl and “heteroar-”, used alone or as part of a larger moiety refer to groups having 5 to 14 ring atoms, preferably 5, 6, or 9 ring atoms; having 6, 10, or 14 ⁇ electrons shared in a cyclic array; and having, in addition to carbon atoms, from one to five heteroatoms.
• heteroatom refers to nitrogen, oxygen, or sulfur, and includes any oxidized form of nitrogen or sulfur, and any quaternized form of a basic nitrogen.
• Heteroaryl groups include, without limitation, thienyl, furanyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolizinyl, purinyl, naphthyridinyl, benzofuranyl and pteridinyl.
• heteroaryl and “heteroar-”, as used herein, also include groups in which a heteroaromatic ring is fused to one or more aryl, cycloaliphatic, or heterocyclyl rings, where the radical or point of attachment is on the heteroaromatic ring.
• Nonlimiting examples include indolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl, indazolyl, benzimidazolyl, benzthiazolyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinolizinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, and pyrido[2,3-b]-l,4-oxazin-3(4H)-one.
• a heteroaryl group may be mono- or polycyclic.
• heteroaryl may be used interchangeably with the terms “heteroaryl ring", “heteroaryl group”, or “heteroaromatic”, any of which terms include rings that are optionally substituted.
• heteroarylkyl refers to an alkyl group substituted by a heteroaryl, wherein the alkyl and heteroaryl portions independently are optionally substituted.
• heteroaryl refers to a 5- to 6-membered monocyclic heteroaryl ring having 1 to 3 heteroatoms independently
• 2008376-0144 selected from nitrogen, oxygen, or sulfur, or an 8- to 14-membered bicyclic heteroaryl ring having 1 to 4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
• heterocycle As used herein, the terms “heterocycle”, “heterocyclyl”, “heterocyclic radical”, and “heterocyclic ring” are used interchangeably and refer to a stable 5- to 7-membered monocyclic or 7-14-membered bicyclic heterocyclic moiety that is saturated, partially unsaturated, or aromatic and having, in addition to carbon atoms, one or more, preferably one to four, heteroatoms, as defined above.
• nitrogen includes a substituted nitrogen.
• the nitrogen in a saturated or partially unsaturated ring having 0-3 heteroatoms selected from oxygen, sulfur or nitrogen, the nitrogen may be N (as in 3,4-dihydro-2H-pyrrolyl), ⁇ (as in pyrrolidinyl), or 3 ⁇ 4fR (as in N-substituted pyrrolidinyl).
• the term "3- to 7-membered heterocyclic” refers to a 3- to 7-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1 to 2 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
• the term "3- to 8- membered heterocyclic” refers to a 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1 to 2 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
• a heterocyclic ring can be attached to its pendant group at any heteroatom or carbon atom that results in a stable structure and any of the ring atoms can be optionally substituted.
• saturated or partially unsaturated heterocyclic radicals include, without limitation, tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl,
• heterocyclic radical are used interchangeably herein, and also include groups in which a heterocyclyl ring is fused to one or more aryl, heteroaryl, or cycloaliphatic rings, such as indolinyl, 3H-indolyl, chromanyl, phenanthridinyl, or tetrahydroquinolinyl, where the radical or point of attachment is on the heterocyclyl ring.
• a heterocyclyl group may be mono- or bicyclic.
• heterocyclylalkyl refers to an alkyl group substituted by a
• acyl refers to a group having a formula -C(0)R where R is hydrogen or an optionally substituted aliphatic, aryl, or heterocyclic group.
• R is hydrogen or an optionally substituted aliphatic, aryl, or heterocyclic group.
• partially unsaturated refers to a ring moiety that includes at least one double or triple bond.
• partially unsaturated is intended to encompass rings having multiple sites of unsaturation, but is not intended to include aryl or heteroaryl moieties, as herein defined.
• protecting group it is meant that a particular functional moiety, e.g., O, S, or N, is masked or blocked, permitting, if desired, a reaction to be carried out selectively at another reactive site in a multifunctional compound.
• a protecting group reacts selectively in good yield to give a protected substrate that is stable to the projected reactions; the protecting group is preferably selectively removable by readily available, preferably non-toxic reagents that do not attack the other functional groups; the protecting group forms a separable derivative (more preferably without the generation of new stereogenic centers); and the protecting group will preferably have a minimum of additional functionality to avoid further sites of reaction.
• oxygen, sulfur, nitrogen, and carbon protecting groups may be utilized.
• hydroxyl protecting groups include methyl, methoxylmethyl (MOM), methylthiomethyl (MTM), ?-butylthiomethyl, (phenyldimethylsilyl)methoxymethyl (SMOM), benzyloxymethyl (BOM), -methoxybenzyloxymethyl (PMBM), (4- methoxyphenoxy)methyl (p-AOM), guaiacolmethyl (GUM), ?-butoxymethyl, 4- pentenyloxymethyl (POM), siloxymethyl, 2-methoxyethoxymethyl (MEM),
• 2,2,2-trichloroethoxymethyl bis(2-chloroethoxy)methyl, 2-(trimethylsilyl)ethoxymethyl (SEMOR), tetrahydropyranyl (THP), 3-bromotetrahydropyranyl, tetrahydrothiopyranyl, 1-methoxycyclohexyl, 4-methoxytetrahydropyranyl (MTHP), 4- methoxytetrahydrothiopyranyl, 4-methoxytetrahydrothiopyranyl S,S-dioxide,
• the protecting groups include methylene acetal, ethylidene acetal,
• N-cyclohexylideneamine N-(5,5-dimethyl-3-oxo-l-cyclohexenyl)amine
• N-borane derivative N-diphenylborinic acid derivative
• N-[phenyl(pentacarbonylchromium- or tungsten)carbonyl] amine N-copper chelate, N-zinc chelate, N-nitroamine
• benzenesulfenamide o-nitrobenzenesulfenamide (Nps), 2,4-dinitrobenzenesulfenamide, pentachlorobenzenesulfenamide, 2-nitro-4-methoxybenzenesulfenamide,
• triphenylmethylsulfenamide 3-nitropyridinesulfenamide (Npys), -toluenesulfonamide (Ts), benzenesulfonamide, 2,3,6,-trimethyl-4-methoxybenzenesulfonamide (Mtr), 2,4,6- trimethoxybenzenesulfonamide (Mtb), 2,6-dimethyl-4-methoxybenzenesulfonamide
• 2008376-0144 (NOV-029-PCT) (Pme), 2,3,5,6-tetramethyl-4-methoxybenzenesulfonamide (Mte), 4- methoxybenzenesulfonamide (Mbs), 2,4,6-trimethylbenzenesulfonamide (Mts), 2,6- dimethoxy-4-methylbenzenesulfonamide (iMds), 2,2,5,7, 8-pentamethylchroman-6- sulfonamide (Pmc), methanesulfonamide (Ms), ⁇ -trimethylsilylethanesulfonamide (SES), 9-anthracenesulfonamide, 4-(4',8'-dimethoxynaphthylmethyl)benzenesulfonamide
• NMBS benzylsulfonamide, trifluoromethylsulfonamide, and phenacylsulfonamide.
• exemplary protecting groups are detailed herein, however, it will be appreciated that the present invention is not intended to be limited to these protecting groups; rather, a variety of additional equivalent protecting groups can be readily identified using the above criteria and utilized in the method of the present invention. Additionally, a variety of protecting groups are described in Protecting Groups in Organic Synthesis, T. W. Greene and P. G. M. Wuts, 3 rd edition, John Wiley & Sons, 1999, the entirety of which is incorporated herein by reference.
• radical or “optionally substituted radical” is sometimes used.
• radical means a moiety or functional group having an available position for attachment to the structure on which the substituent is bound. In general the point of attachment would bear a hydrogen atom if the substituent were an independent neutral molecule rather than a substituent.
• radical or “optionally-substituted radical” in this context are thus interchangeable with “group” or “optionally-substituted group”.
• compounds of the invention may contain “optionally substituted” moieties.
• substituted whether preceded by the term “optionally” or not, means that one or more hydrogens of the designated moiety are replaced with a suitable substituent.
• an "optionally substituted group'Or “optionally substituted radical” may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituent may be either the same or different at every position.
• Combinations of substituents envisioned by this invention are preferably those that result in the formation of stable or chemically feasible compounds.
• stable refers to compounds that are not substantially altered when subjected to conditions to
• 2008376-0144 (NOV-029-PCT) allow for their production, detection, and, in certain embodiments, their recovery, purification, and use for one or more of the purposes disclosed herein.
• substituents are shown attached to a bond that crosses a bond in a ring of the depicted molecule. This convention indicates that one or more of the substituents may be attached to the ring at any available position (usually in place of a hydrogen atom of the parent structure). In cases where an atom of a ring so substituted has two substitutable positions, two groups may be present on the same ring atom. Unless otherwise indicated, when more than one substituent is present, each is defined independently of the others, and each may have a different structure. In cases where the substituent shown crossing a bond of the ring is -R, this has the same meaning as if the ring were said to be "optionally substituted" as described in the preceding paragraph.
• Suitable monovalent substituents on a substitutable carbon atom of an "optionally substituted" group are independently halogen; -(CH 2 )o- 4 R°; -(CH 2 )o- 4 0R°;
• -CH CHPh, which may be substituted with R°; -N0 2 ; -CN; -N 3 ; -(CH 2 ) 0 - 4 N(R o ) 2 ;
• alkylene C(0)0-N(R°) 2 , wherein each R° may be substituted as defined below and is independently hydrogen, Ci-s aliphatic, -CH 2 Ph, -O(CH 2 ) 0 -iPh, or a 5-6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently
• 2008376-0144 (NOV-029-PCT) selected from nitrogen, oxygen, or sulfur, or, notwithstanding the definition above, two independent occurrences of R°, taken together with intervening atom(s), form a 3-12- membered saturated, partially unsaturated, or aryl mono- or polycyclic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, which may be substituted as defined below.
• Suitable monovalent substituents on R° are independently halogen, -(CH 2 ) 0 _ 2 R e , -(haloR*), -(CH 2 ) 0 - 2 OH, -(CH 2 ) 0 - 2 OR e , -(CH 2 ) 0 - 2 CH(OR e ) 2 ;
• alkylene)C(0)OR or -SSR" wherein each R* is unsubstituted or where preceded by "halo” is substituted only with one or more halogens, and is independently selected from Ci_ 4 aliphatic, -CH 2 Ph, -O(CH 2 ) 0 -iPh, or a 5-6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
• Suitable divalent substituents that are bound to vicinal substitutable carbons of an "optionally substituted” group include: -0(CR * 2 ) 2 _ 3 0-, wherein each independent occurrence of R is selected from hydrogen, Ci_6 aliphatic which may be substituted as defined below, or an unsubstituted 5-6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
• Suitable substituents on the aliphatic group of R include halogen, -R", -(haloR"), -OH, -OR", -O(haloR'), -CN, -C(0)OH, -C(0)OR e , -NH 2 , -NHR", -NR' 2 , or -N0 2 , wherein each R* is unsubstituted or where preceded by "halo" is substituted only with one or more halogens, and is independently C1-4 aliphatic, -CH 2 Ph, -O(CH 2 ) 0 -iPh, or a 5- 6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
• Suitable substituents on a substitutable nitrogen of an "optionally substituted" group include -R ⁇ , -NR ⁇ 2 , -C(0)R ⁇ , -C(0)OR ⁇ , -C(0)C(0)R ⁇ , -C(0)CH 2 C(0)R ⁇ ,
• each R ⁇ is independently hydrogen, Ci_6 aliphatic which may be substituted as defined below, unsubstituted -OPh, or an unsubstituted 5-6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or, notwithstanding the definition above, two independent occurrences of R ⁇ , taken together with intervening atom(s) form an unsubstituted 3-12-membered saturated, partially unsaturated, or aryl mono- or bicyclic ring having 0-4 heteroatoms
• a substitutable nitrogen may be substituted with three R ⁇ substituents to provide a charged ammonium moiety -N + (R ⁇ )3, wherein the ammonium moiety is further complexed with a suitable counterion.
• Suitable substituents on the aliphatic group of R ⁇ are independently halogen, -R e , -(haloR*), -OH, -OR", -0(haloR e ), -CN, -C(0)OH, -C(0)OR e , -NH 2 , -NHR*, -NR' 2 , or
• each R* is unsubstituted or where preceded by "halo" is substituted only with one or more halogens, and is independently C1-4 aliphatic, -CH 2 Ph, -O(CH 2 ) 0 -iPh, or a 5-6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
• halo is substituted only with one or more halogens, and is independently C1-4 aliphatic, -CH 2 Ph, -O(CH 2 ) 0 -iPh, or a 5-6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
• catalyst refers to a substance the presence of which increases the rate and/or extent of a chemical reaction, while not being consumed or undergoing a permanent chemical change itself.
• multidentate refers to ligands having multiple sites capable of coordinating to a single metal center.
• activating moiety refers to a moiety comprising one or more activating functional groups.
• an activating moiety improves the catalytic activity of a metal complex.
• such improved catalytic activity is characterized by higher conversion of starting materials compared to a metal complex lacking an activating moiety.
• such improved catalytic activity is characterized by higher rate of conversion of starting materials compared to a metal complex lacking an activating moiety.
• such improved catalytic activity is characterized by higher yield of product compared to a metal complex lacking an activating moiety.
• the present invention encompasses the recognition that there remains a need for metal complexes useful in the copolymerization of epoxides and carbon dioxide.
• Metal complexes provided by the present invention can show significant advantages for uses in the copolymerization of epoxides and carbon dioxide. While not wishing to be bound by any particular theory, it is believed that metal complexes of the present invention provide enhanced reactivity and/or selectivity when compared to known metal complexes. In certain embodiments, a provided metal complex is highly selective for a
• a provided metal complex is highly selective for polycarbonate formation.
• the present invention provides, among other things, metal complexes for the copolymerization of carbon dioxide and epoxides and methods of using the same.
• provided metal complexes contain two or more metal atoms.
• the metal atoms are complexed to one or more multidentate ligands and at least one tethered activating moiety tethered to one or more of the ligands.
• an activating moiety comprises a linker and one or more activating functional groups.
• at least one activating functional group present on the tethered moiety can act as a polymerization co-catalyst and thereby increase the rate of the copolymerization.
• provided metal complexes act as polymerization catalysts.
• the present invention provides multi-metal complexes and methods for using the same in the copolymerization of carbon dioxide and epoxides.
• provided metal complexes have a structure C-l:
• M 1 is a first metal atom
• M 2 is a second metal atom
• w' (Z) m represents one or more activating moieties attached to the multidentate ligand system, where— ⁇ * ⁇ is a linker moiety covalently coupled to the ligand system, each Z is an activating functional group; and m is an integer from 1 to 4 representing the number of Z groups present on an individual linker moiety.
• each activating moiety— ⁇ TM ⁇ (Z) m comprises a linker "— " coupled to at least one activating functional group Z as described above, with m denoting the number of activating functional groups present on a single linker moiety.
• each activating moiety may contain more than one activating functional group Z.
• each linker moiety— ⁇ contains 1-30 atoms including at least one carbon atom, and optionally one or more atoms selected from the group consisting of N, O, S, Si, B, and P.
• each R y is independently -H, or an optionally substituted radical selected from the group consisting of Ci-6 aliphatic, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, a 3-7 membered saturated or partially unsaturated monocyclic heterocyclic ring having 1 -2 heteroatoms
• a linker moiety is a C4-C12 aliphatic group substituted with one or more moieties selected from the group consisting of halogen, -N0 2 , -CN, -SR y , -S(0)R y , -S(0) 2 R y , -NR y C(0)R y , -OC(0)R y , -C0 2 R y , -NCO, -N 3 , -OR 4 ,
• R y and R 4 is independently as defined above and described in classes and subclasses herein.
• a linker moiety is an optionally substituted C3-C30 aliphatic group. In certain embodiments, a linker is an optionally substituted C 4 _ 2 4 aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C 4 _ C 2 o aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C 4 _Ci 2 aliphatic group. In certain embodiments, a linker is an optionally substituted C 4 _io aliphatic group. In certain embodiments, a linker is an optionally substituted C 4 _8 aliphatic group.
• a linker moiety is an optionally substituted C4.Ce aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C6-Ci 2 aliphatic group. In certain embodiments, a linker moiety is an optionally substituted Cs aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C7 aliphatic group. In certain embodiments, a linker moiety is an optionally substituted Ce aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C5 aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C 4 aliphatic group.
• a linker moiety is an optionally substituted C3 aliphatic group.
• a aliphatic group in the linker moiety is an optionally substituted straight alkyl chain.
• the aliphatic group is an optionally substituted branched alkyl chain.
• a linker moiety is a C 4 to C 2 o alkyl group having one or more methylene groups replaced by -C(R°) 2 - wherein R° is as defined above.
• a linker moiety consists of a bivalent aliphatic group having 4 to 30 carbons including one or more Ci_ 4 alkyl substituted carbon atoms.
• a linker moiety consists of a bivalent aliphatic group having 4 to 30 carbons including one or more gem-dimethyl substituted carbon atoms.
• a linker moiety includes one or more optionally substituted cyclic elements selected from the group consisting of saturated or partially unsaturated carbocyclic, aryl, heterocyclic, or heteroaryl. In certain embodiments, a
• linker moiety consists of the substituted cyclic element, in some embodiments the cyclic element is part of a linker with one or more non-ring heteroatoms or optionally substituted aliphatic groups comprising other parts of the linker moiety.
• a linker moiety is of sufficient length to allow one or more activating functional groups to be positioned near a metal atom of a metal complex.
• structural constraints are built into a linker moiety to control the disposition and orientation of one or more activating functional groups near a metal center of a metal complex.
• such structural constraints are selected from the group consisting of cyclic moieties, bicyclic moieties, bridged cyclic moieties and tricyclic moieties.
• such structural constraints are the result of acyclic steric interactions.
• steric interactions due to syn-pentane, gauche-butane, and/or allylic strain in a linker moiety bring about structural constraints that affect the orientation of a linker and one or more activating groups.
• structural constraints are selected from the group consisting of cis double bonds, trans double bonds, cis allenes, trans allenes, and triple bonds.
• structural constraints are selected from the group consisting of substituted carbons including geminally disubstituted groups such as sprirocyclic rings, gem dimethyl groups, gem diethyl groups and gem diphenyl groups.
• structural constraints are selected from the group consisting of heteratom-containing functional groups such as sulfoxides, amides, and oximes.
• linker moieties are selected from the group consisting of:
• each s is independently 0-6, t is 0-4, R y as defined above and described in classes and subclasses herein, * represents the site of attachment to a ligand, and each # represents a site of attachment of an activating functional group.
• s is 0. In some embodiments, s is 1. In some
• s is 2. In some embodiments, s is 3. In some embodiments, s is 4. In some embodiments, s is 5. In some embodiments, s is 6.
• t is 1. In some embodiments, t is 2. In some
• t is 3. In some embodiments, t is 4.
• an activating functional group is selected from the group consisting of neutral nitrogen-containing functional groups, cationic moieties, phosphorous-containing functional groups, and combinations of two or more of these.
• one or more tethered activating functional groups on provided metal complexes are neutral nitrogen-containing moieties.
• such moieties include one or more of the structures in Table Z-l :
• each R 1 and R 2 is independently hydrogen or an optionally substituted radical selected from the group consisting of C 1-20 aliphatic; C 1-20 heteroaliphatic; a 3- to 8- membered saturated or partially unsaturated monocyclic carbocycle; a 7- to 14- membered saturated or partially unsaturated polycyclic carbocycle; a 5- to 6- membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; an 8- to 14-membered polycyclic heteroaryl ring having 1 -5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 14-membered saturated or partially unsaturated polycyclic heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; phenyl; or an 8- to 14-member
• each R 4 is independently hydrogen, a hydroxyl protecting group, or an optionally substituted radical selected from the group consisting of C 1-20 acyl; C 1-20 aliphatic; Ci-20 heteroaliphatic; a 3 - to 8-membered saturated or partially unsaturated monocyclic carbocycle; a 7- to 14-membered saturated or partially unsaturated polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; an 8- to 14- membered polycyclic heteroaryl ring having 1 -5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3 - to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 14-membered saturated or partially unsaturated polycyclic heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
• each R 1 group is the same. In other embodiments, R 1 groups are different. In certain embodiments, R 1 is hydrogen. In some embodiments, R 1 is an optionally substituted radical selected from the group consisting of C 1-20 aliphatic; C 1-20 heteroaliphatic, 5- to 14-membered heteroaryl, phenyl, 8- to 10-membered aryl and 3- to 7-membered heterocyclic.
• R 1 is an optionally substituted radical selected from the group consisting of a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle; a 7- to 14-membered saturated or partially unsaturated polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; an 8- to 14- membered polycyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 14-membered saturated or partially unsaturated polycyclic heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; phenyl; or an 8- to 14-membered polycyclic aryl ring.
• R 1 is an optionally substituted radical selected from the group consisting of C 1-12 aliphatic and C 1-12 heteroaliphatic. In some embodiments, R 1 is optionally substituted C 1-20 aliphatic. In some embodiments, R 1 is optionally substituted
• R 1 is optionally substituted Ci_6 aliphatic. In some embodiments, R 1 is optionally substituted Ci-20 heteroaliphatic. In some embodiments, R 1 is optionally substituted Ci-12 heteroaliphatic. In some embodiments, R 1 is optionally substituted phenyl. In some embodiments, R 1 is optionally substituted 8- to 10- membered aryl. In some embodiments, R 1 is an optionally substituted 5- to 6-membered heteroaryl group. In some embodiments, R 1 is an optionally substituted 8- to 14- membered polycyclic heteroaryl group. In some embodiments, R 1 is optionally substituted 3- to 8-membered heterocyclic.
• each R 1 is independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl.
• R 1 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl.
• R 1 is butyl.
• R 1 is isopropyl.
• R 1 is neopentyl.
• R 1 is perfluoro.
• R 1 is -CF 2 CF 3 .
• R 1 is phenyl. In some embodiments, R 1 is benzyl.
• each R 2 group is the same. In other embodiments, R 2 groups are different. In certain embodiments, R 2 is hydrogen. In some embodiments, R 2 is an optionally substituted radical selected from the group consisting of Ci-20 aliphatic; Ci-20 heteroaliphatic, 5- to 14-membered heteroaryl, phenyl, 8- to 10-membered aryl and 3- to 7-membered heterocyclic.
• R 2 is an optionally substituted radical selected from the group consisting of a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle; a 7- to 14-membered saturated or partially unsaturated polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; an 8- to 14- membered polycyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 14-membered saturated or partially unsaturated polycyclic heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; phenyl; or an 8- to 14-membered polycyclic aryl ring.
• R 2 is an optionally substituted radical selected from the group consisting of C 1-12 aliphatic and C 1-12 heteroaliphatic. In some embodiments, R 2 is optionally substituted C 1-20 aliphatic. In some embodiments, R 2 is optionally substituted Ci-12 aliphatic. In some embodiments, R 2 is optionally substituted C e aliphatic. In some embodiments, R 2 is optionally substituted C 1-20 heteroaliphatic. In some embodiments, R 2 is optionally substituted C 1-12 heteroaliphatic. In some embodiments, R 2 is optionally substituted phenyl. In some embodiments, R 2 is optionally substituted 8- to 10- membered aryl.
• R 2 is an optionally substituted 5- to 6-membered heteroaryl group. In some embodiments, R 2 is an optionally substituted 8- to 14- membered polycyclic heteroaryl group. In some embodiments, R 2 is optionally substituted 3- to 8-membered heterocyclic.
• each R 2 is indepedendently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl.
• R 2 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl.
• R 2 is butyl.
• R 2 is isopropyl.
• R 2 is neopentyl.
• R 2 is perfluoro.
• R 2 is -CF 2 CF 3 .
• R 2 is phenyl. In some embodiments, R 2 is benzyl.
• each R 1 and R 2 are hydrogen. In some embodiments, each R 1 is hydrogen each and each R 2 is other than hydrogen. In some embodiments, each R 2 is hydrogen each and each R 1 is other than hydrogen.
• R 1 and R 2 are both methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R 1 and R 2 are each butyl. In some embodiments, R 1 and R 2 are each isopropyl. In some embodiments, R 1 and R 2 are each perfluoro. In some embodiments, R 1 and R 2 are -CF2CF 3 . In some
• R 1 and R 2 are each phenyl. In some embodiments, R 1 and R 2 are each benzyl.
• R 1 and R 2 are taken together with intervening atoms to form one or more optionally substituted carbocyclic, heterocyclic, aryl, or heteroaryl rings. In certain embodiments, R 1 and R 2 are taken together to form a ring fragment
• 2008376-0144 selected from the group consisting of: -C(R y ) 2 -, -C(R y ) 2 C(R y ) 2 -, -C(R y ) 2 C(R y ) 2 C(R y ) 2 -, -C(R y ) 2 OC(R y ) 2 -, and -C(R y ) 2 NR y C(R y ) 2 -, wherein R y is as defined above.
• R 1 and R 2 are taken together to form a ring fragment selected from the group consisting of: -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 OCH 2 -, and -CH 2 NR y CH 2 -.
• R 1 and R 2 are taken together to form an unsaturated linker moiety optionally containing one or more additional heteroatoms.
• the resulting nitrogen-containing ring is partially unsaturated.
• the resulting nitrogen-containing ring comprises a fused polycyclic heterocycle.
• R 3 is H. In certain embodiments, R 3 is optionally C 1-20 aliphatic; C 1-20 heteroaliphatic, 5- to 14-membered heteroaryl, phenyl, 8- to 10-membered aryl or 3- to 7-membered heterocyclic.
• R 3 is an optionally substituted radical selected from the group consisting of a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle; a 7- to 14-membered saturated or partially unsaturated polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; an 8- to 14-membered polycyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3 - to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 14-membered saturated or partially unsaturated polycyclic heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; phenyl; or an 8- to 14-membered polycyclic aryl ring.
• R 3 is optionally substituted C 1-12 aliphatic.
• R 3 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R 3 is butyl. In some embodiments, R 3 is isopropyl. In some embodiments, R 3 is perfluoro. In some embodiments, R 3 is -CF 2 CF 3 .
• one or more R 1 or R 2 groups are taken together with R 3 and intervening atoms to form an optionally substituted heterocyclic or heteroaryl ring.
• R 1 and R 3 are taken together to form an optionally substituted 5- or
• R 2 and R 3 are taken together to form an optionally substituted 5- or 6-membered ring optionally containing one or more additional heteroatoms.
• R 1 , R 2 and R 3 are taken together to form an optionally substituted fused ring system.
• such rings formed by combinations of any of R 1 , R 2 and R 3 are partially unsaturated or aromatic.
• R 4 is hydrogen. In some embodiments, R 4 is an optionally substituted radical selected from the group consisting of C 1-12 aliphatic, phenyl, 8- to 10-membered aryl, and 3- to 8-membered heterocyclic. In certain embodiments, R 4 is a C 1-12 aliphatic. In certain embodiments, R 4 is a Ci_6 aliphatic. In some embodiments, R 4 is an optionally substituted 8- to 10-membered aryl group. In certain embodiments, R 4 is optionally substituted C 1-12 acyl or in some embodiments, optionally substituted Ci_6 acyl. In certain embodiments, R 4 is optionally substituted phenyl.
• R 4 is a hydroxyl protecting group. In some embodiments, R 4 is a silyl protecting group. In some embodiments, R 4 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, allyl, phenyl or benzyl.
• R 1 and R 4 are taken together with intervening atoms to form one or more optionally substituted heterocyclic or heteroaryl rings optionally containing one or more additional heteroatoms.
• an activating functional group is an N-linked amino
• R 1 and R 2 are as defined above and described in classes and subclasses herein.
• an N-linked amino activating functional group is selected from the group consisting of:
• one or more activating functional groups is an N-linked
• R hydroxyl amine derivative OR 4 , wherein R 1 and R 4 are as defined above and described in classes and subclasses herein.
• one or more N-linked hydroxyl amine activating functional groups are selected from the group consisting of:
• an activating functional group in a provided metal complex is an amidine. In certain embodiments, such amidine activating functional
• R 1 , R 2 , and R 3 is as defined above and described in classes and subclasses herein.
• an activating functional group is an N-linked amidine:
• activating functional groups are amidine moieties linked
• imine nitrogen: N K wherein each of R , , and R is as defined above and described in classes and subclasses herein.
• imine-linked amidine activating functional groups are selected from the group consisting of:
• carbon-linked amidine activating groups are selected from the group consisting of:
• one or more activating functional groups is a carbamate.
• a carbamate is N-linked: , wherein each of R 1 and is as defined above and described in classes and subclasses herein.
• a carbamate is , wherein each of R and R is as defined above and described in classes and subclasses herein.
• R 2 is selected from the group consisting of: methyl, ?-butyl, ?-amyl, benzyl, adamantyl, allyl, 4-methoxycarbonylphenyl,
• an activating functional group is a guanidine or bis- uanidine grou :
• each R 1 and R 2 is as defined above and described in classes and subclasses herein.
• any two or more R 1 or R 2 groups are taken together with intervening atoms to form one or more optionally substituted carbocyclic, heterocyclic, aryl, or heteroaryl rings.
• R 1 and R 2 groups are taken together to form an optionally substituted 5- or 6-membered ring.
• three or more R 1 and/or R 2 groups are taken together to form an optionally substituted fused ring system.
• an activating functional group is a guanidine or bis guanidine moiety, it is selected from the group consisting of:
• an activating functional group is a urea: , wherein each R 1 and R 2 is independently as defined above and described in classes and subclasses herein.
• activating functional groups are oxime or hydrazone
• R 1 , R 2 , R 3 , and R 4 are as defined above and described in classes and subclasses herein.
• an activating functional group is an N-oxide derivative:
• each of R 1 and R 2 is as defined above and described in classes and subclasses herein.
• an N-oxide activating functional group is selected from the group consisting of:
• one or more tethered activating functional groups on provided metal complexes comprise a cationic moiety.
• a cationic moiety is selected from a structure in Table Z-2:
• each of R 1 , R 2 , and R 3 is independently as defined above and described in classes and subclasses herein;
• R 5 is R 2 or hydroxyl; wherein R 1 and R 5 can be taken together with intervening atoms to form one or more optionally substituted carbocyclic, heterocyclic, aryl, or heteroaryl rings; each R 6 and R 7 is independently hydrogen or an optionally substituted radical selected from the group consisting of C 1-20 aliphatic; C 1-20 heteroaliphatic; a 3- to 8- membered saturated or partially unsaturated monocyclic carbocycle; a 7- to 14- membered saturated or partially unsaturated polycyclic carbocycle; a 5- to 6- membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; an 8- to 14-membered polycyclic heteroaryl ring having 1 -5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 14-membered saturated
• 2008376-0144 selected from nitrogen, oxygen, or sulfur; a 3 - to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1 -3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 14-membered saturated or partially unsaturated polycyclic heterocycle having 1 -5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; phenyl; or an 8- to 14- membered polycyclic aryl ring; wherein each R y is independently as defined above and described in classes and subclasses herein, and where two or more adjacent R 8 groups can be taken together to form an optionally substituted saturated, partially unsaturated, or aromatic 5- to 12-membered ring containing 0 to 4 heteroatoms;
• X " is any anion
• Ring A is an optionally substituted, 5- to 10-membered heteroaryl group
• Ring B is an optionally substituted, 3- to 8-membered saturated or partially
• unsaturated monocyclic heterocyclic ring having 0-2 heteroatoms in addition to the depicted ring nitrogen atom independently selected from nitrogen, oxygen, or sulfur.
• a cationic activating functional group is a protonated
• amine is as defined above and described in classes and subclasses herein.
• a protonated amine activating functional group is selected from the group consisting of:
• an activating functional group is a guanidinium group:
• each R 1 and R 2 is independently as defined above and described in classes and subclasses herein.
• each R 1 and R 2 is independently hydrogen or C 1-20 aliphatic.
• each R 1 and R 2 is independently hydrogen or C 1-12 aliphatic.
• each R 1 and R 2 is independently hydrogen or C 1-20 heteroaliphatic.
• each R 1 and R 2 is
• each R 1 and R 2 is independently hydrogen or phenyl. In some embodiments, each R 1 and R 2 is
• each R 1 and R 2 is independently hydrogen or 8- to 10-membered aryl. In some embodiments, each R 1 and R 2 is independently hydrogen or 5- to 10-membered heteroaryl. In some embodiments, each R 1 and R 2 is independently hydrogen or 3- to 7-membered heterocyclic. In some embodiments, one or more of R 1 and R 2 is optionally substituted C 1-12 aliphatic.
• any two or more R 1 or R 2 groups are taken together with intervening atoms to form one or more optionally substituted carbocyclic, heterocyclic, aryl, or heteroaryl rings.
• R 1 and R 2 groups are taken together to form an optionally substituted 5- or 6-membered ring.
• three or more R 1 and/or R 2 groups are taken together to form an optionally substituted fused ring system.
• a R 1 and 2 group are taken together with intervening
• Ring G is an optionally substituted 5- to 7-membered saturated or partially unsaturated heterocyclic ring.
• a guanidinium activating functional group is selected from the group consisting of:
• an activating functional group is a sulfonium group or an
• arsonium group R or ⁇ , wherein each of R 1 , R 2 , and R 3 are as defined above and described in classes and subclasses herein.
• an arsonium activating functional group is selected from the group consisting of:
• an activating functional group is an optionally substituted nitrogen-containing heterocycle.
• the nitrogen-containing heterocycle is an aromatic heterocycle.
• the optionally substituted nitrogen-containing heterocycle is selected from the group consisting of: pyridine, imidazole, pyrrolidine, pyrazole, quinoline, thiazole, dithiazole, oxazole, triazole, pyrazolem, isoxazole, isothiazole, tetrazole, pyrazine, thiazine, and triazine.
• a nitrogen-containing heterocycle includes a quaternarized nitrogen atom.
• I ning heterocycle includes an
• the optionally substituted nitrogen-containing heterocycle is selected from the group consisting of pyridinium, imidazolium, pyrrolidinium, pyrazolium, quinolinium, thiazolium, dithiazolium, oxazolium, triazolium, isoxazolium, isothiazolium, tetrazolium,
• a nitrogen-containing heterocycle is linked to a metal complex via a ring nitrogen atom.
• a ring nitrogen to which the attachment is made is thereby quaternized, and in some embodiments, linkage to a metal complex takes the place of an N-H bond and the nitrogen atom thereby remains neutral.
• an optionally substituted N-linked nitrogen-containing heterocycle is a pyridinium derivative.
• optionally substituted N- linked nitrogen-containing heterocycle is an imidazolium derivative.
• optionally substituted N-linked nitrogen-containing heterocycle is a thiazolium derivative.
• optionally substituted N-linked nitrogen- containing heterocycle is a pyridinium derivative.
• an activating functional group is .
• ring A is an optionally substituted, 5- to 10-membered heteroaryl group.
• Ring A is an optionally substituted, 6-membered heteroaryl group.
• Ring A is a ring of a fused heterocycle.
• Ring A is an optionally substituted pyridyl group.
• ring A is other than an imidazole, an oxazole, or a thiazole.
• a nitrogen-containing heterocycle activating functional group is selected from the group consisting of:
• Ring B is a 5 -membered saturated or partially
• Ring B is a 6- membered saturated or partially unsaturated heterocycle. In certain embodiments, Ring B is a 7-membered saturated or partially unsaturated heterocycle. In certain
• Ring B is tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, pyrrolidonyl, piperidinyl, pyrrolinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl,
• Ring B is piperidinyl.
• an activating functional group is
• R 1 , R 2 , and R 3 is independently as defined above and described in classes and subclasses herein.
• an activating functional group is , wherein each R 1 and R 2 is independently as defined above and described in classes and subclasses herein.
• an activating functional group is R R , wherein each of R 1 , R 2 , R 6 , and R 7 is as defined above and described in classes and subclasses herein.
• R 6 and R 7 are each independently an optionally substituted group selected from the group consisting of C 1-20 aliphatic; C 1-20
• R 6 and R 7 are each independently an optionally substituted C 1-20 aliphatic. In some embodiments, R 6 and R 7 are each independently an optionally substituted C 1-20 heteroaliphatic having. In some embodiments, R 6 and R 7 are each independently an optionally substituted phenyl or
• R 6 and R 7 are each independently an optionally substituted 5- tolO-membered heteroaryl.
• R 6 and R 7 can be taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C3-C14 carbocycle, optionally substituted C3- Ci4 heterocycle, optionally substituted C6-C1 0 aryl, and optionally substituted 5- to 10- membered heteroaryl.
• R 6 and R 7 are each independently an optionally substituted Ci_6 aliphatic.
• each occurrence of R 6 and R 7 is independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or benzyl. In some embodiments, each occurrence of R 6 and R 7 is independently perfluoro. In some embodiments, each occurrence of R 6 and R 7 is independently -CF 2 CF 3 .
• an activating functional group is R R i R 1 wherein each R 1 and R 2 is independently as defined above and described in classes and subclasses herein.
• an activating functional group is wherein each R 1 , R 2 , and R 3 is independently as defined above and described in classes and subclasses herein.
• an activating functional group is
• each R 1 and R 2 is independently as defined above and described in classes and subclasses herein.
• an activating functional group is R R wherein each R 1 and R 2 is independently as defined above and described in classes and subclasses herein.
• an activating functional group is wherein each R 1 , R 2 , and R 3 is independently as defined above and described in classes and subclasses herein. an activating functional group is
• each R 1 and R 2 is independently as defined above and described in classes and subclasses herein.
• X is any anion. In certain embodiments, X is a nucleophile. In some embodiments, X is a nucleophile capable of ring opening an epoxide. In certain embodiments, X is absent. In certain embodiments, X is a nucleophilic ligand.
• X is -OR x , wherein R x is selected from optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, and optionally substituted heteroaryl.
• X is -OR x , wherein R x is optionally substituted aryl. In certain embodiments, X is -OR x , wherein R x is optionally substituted phenyl. In certain embodiments, X is -OC 6 H 5 or -OC 6 H 2 (2,4- 0 2 ).
• X is halo. In certain embodiments, X is -Br. In certain embodiments, X is -CI. In certain embodiments, X is -I.
• X is -0(S0 2 )R x . In certain embodiments X is -OTs. In certain embodiments X is -OSC ⁇ Me. In certain embodiments X is -OSO 2 CF 3 . In some embodiments, X is a 2,4-dinitrophenolate anion.
• activating functional groups Z are phosphorous containing groups.
• a phosphorous-containing functional group is chosen from the group consisting of: phosphines (-PR y 2); Phosphine oxides -P(0)R y 2;
• a phosphorous-containing functional group is chosen from the group consisting of:
• each R 1 , R 2 , and R 4 is as defined above and described in classes and
• intervening atoms to form an optionally substituted ring optionally containing one or more heteroatoms, or an R 4 group can be taken with an R 1 or R 2 group to an optionally substituted carbocyclic, heterocyclic, heteroaryl, or aryl ring.
• phosphorous containing functional groups include those disclosed in The Chemistry of Organophosphorus Compounds. Volume 4. Ter- and Quinquevalent Phosphorus Acids and their Derivatives. The Chemistry of Functional Group Series Edited by Frank R. Hartley (Cranfield University, Cranfield, U.K.). Wiley: New York. 1996. ISBN 0-471-95706-2, the entirety of which is hereby incorporated herein by reference.
• phosphorous containing functional groups have the formula:
• W is any anion, and n is an integer between 1 and 4.
• an activating functional group is a phosphonate group: , wherein each R 1 , R 2 , and R 4 is independently as defined above and described in classes and subclasses herein.
• a phosphonate activating functional group is selected from the group consisting of:
• an activating functional group is a phosphonic diamide
• each R 1 and R 2 group in a phosphonic diamide is methyl.
• an activating functional group is a phosphine group: wherein R 1 , and R 2 are as defined above and described in classes and subclasses herein.
• a phosphine activating functional group is selected from the group consisting of:
• the present invention provides bimetallic compl methods of using the same, wherein:
• an activating group is selected from the group consisting of
• an activating group is A :
• an activating group is ⁇ xvi) an activating group is
• an activating group is xxiii) an activating group is
• an activating group is s O R
• an activating group is xxxi) an activating group is r2
• each R 1 group is the same; xxxiii) for subsets i) through xxxi), each R 1 group is hydrogen; xxxiv) for subsets i) through xxxi), at least one R 1 group is different from other R 1 groups; xxxv) for subsets i) through xxxi), R 1 is optionally substituted Ci-20 aliphatic; xxxvi) for subsets i) through xxxi), each R 1 is independently hydrogen, -CF 2 CF 3 , methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl; xxxvii) for subsets i) through xxxvi), each R 2 group is the same; xxxvii) for subsets i) through xxxvi), each R 2 group is the same; xxxii) for sub
• 2008376-0144 (NOV-029-PCT) xlvi) for any of subsets i) through xliii) having R 3 , R 3 is independently hydrogen, - CF 2 CF 3 , methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl; xlvii) for any of subsets i) through xliii) having R 3 , one or more R 1 or R 2 groups are taken together with R 3 and intervening atoms to form an optionally substituted heterocyclic or heteroaryl ring; xlviii) for any of subsets i) through xlviii) having R 4 , R 4 is hydrogen; xlix) for any of subsets i) through xlviii) having R 4 , R 4 is optionally substituted Ci_ 12 aliphatic;
• Ring A is a 5- to 6-membered heteroaryl group
• the present invention provides metal complexes that include two metal atoms coordinated to a multidentate ligand system and at least one activating moiety tethered to a ligand.
• provided metal complexes have a structure C-1:
• M 1 is a first metal atom
• M 2 is a second metal atom
• (Z)TM represents one or more activating moieties attached to the multidentate ligand system, where— is a linker moiety covalently coupled to the ligand system, each Z is an activating functional group; and m is an integer from 1 to 4 representing the number of Z groups present on an individual linker moiety.
• provided metal complexes include two metal atoms coordinated to a multidentate ligand system and at least one activating moiety tethered to
• 2008376-0144 (NOV-029-PCT) a multidentate ligand system.
• there are 1 to 10 activating moieties there are 1 to 10 activating moieties
• ⁇ ⁇ " ( z )m tethered to a multidentate ligand there are 1 to 8 such activating moieties tethered to a multidentate ligand. In certain embodiments, there are 1 to 4 such activating moieties tethered to the multidentate ligand.
• a multidentate ligand is formed by reacting two equivalents of a dialdehyde (optionally comprising a " ⁇ ( z )m activating moiety) with two equivalents of a diamine (optionally comprising a ⁇ m activating moiety).
• multidentate ligands may be combined (in some embodiments in situ) with two equivalents of a metal ion to form a bimetallic complex.
• M 1 is a metal atom selected from periodic table groups 3- 13, inclusive. In certain embodiments, M 1 is a transition metal selected from periodic table groups 5-12, inclusive. In certain embodiments, M 1 is a transition metal selected from periodic table groups 4-11, inclusive. In certain embodiments, M 1 is a transition metal selected from periodic table groups 5-10, inclusive. In certain embodiments, M 1 is a transition metal selected from periodic table groups 7-9, inclusive. In some
• M 1 is selected from the group consisting of Cr, Mn, V, Fe, Co, Mo, W, Ru, Al, and Ni.
• M 1 is a metal atom selected from the group consisting of: cobalt; chromium; aluminum; titanium; ruthenium, and manganese.
• M 1 is cobalt.
• M 1 is chromium.
• M 1 is aluminum. In some embodiments, M 1 is zinc.
• M 2 is a metal atom selected from periodic table groups 3- 13, inclusive. In certain embodiments, M 2 is a transition metal selected from periodic table groups 5-12, inclusive. In certain embodiments, M 2 is a transition metal selected from periodic table groups 4-11, inclusive. In certain embodiments, M 2 is a transition metal selected from periodic table groups 5-10, inclusive. In certain embodiments, M 2 is a transition metal selected from periodic table groups 7-9, inclusive. In some
• M 2 is selected from the group consisting of Cr, Mn, V, Fe, Co, Mo, W, Ru, Al, and Ni.
• M 2 is a metal atom selected from the group consisting of: cobalt; chromium; aluminum; titanium; ruthenium, and manganese.
• M 2 is cobalt.
• M 2 is chromium.
• M 2 is aluminum. In some embodiments, M 2 is zinc.
• M 1 and M 2 are the same metal. In other embodiments, M 1 and M 2 are different metals. In some embodiments, M 1 and M 2 are both cobalt. In some embodiments, M 1 and M 2 are both chromium. In some embodiments, M 1 and M 2 are both aluminum. In some embodiments, M 1 and M 2 are both zinc.
• a metal complex is dicobalt complex.
• each cobalt atom has an oxidation state of 3+ (i.e., Co(III)).
• at leaset one cobalt metal has an oxidation state of 2+ (i.e., Co(II)).
• one cobalt atom has an oxidation state of 3+ (i.e., Co(III)) and the other cobalt atom has an oxidation state of 2+ (i.e., Co(II)).
• a metal complex comprises two metal atoms coordinated to a single multidentate ligand system and in some
• a metal complex comprises a chelate containing a plurality of individual
• a metal complex contains at least one bidentate ligand. In some embodiments, a metal complex contains at least one tridentate ligand. In some embodiments, a metal complex contains at least one tetradentate ligand. In some embodiments, a metal complex contains a hexadentate ligand.
• a multidentate ligand system in complexes of formula CI in complexes of formula CI
• Q , Q Q Q Q Q Q an d Q are each independently oxygen, nitrogen or sulfur atoms which may be optionally substituted if allowed by valency rules; each is optionally present and independently represents an optionally substituted bridge containing 2 to 20 carbon atoms, wherein such bridges can independently, or in combination, optionally form one or more optionally substituted rings, wherein each bridge present optionally contains one or more heteroatoms; and one or more groups is optionally substituted with one or more wherein each is independently an activating moiety as defined above and
• 2008376-0144 (NOV-029-PCT) moiety is independently an optionally substituted carbon bridge that is optionally unsaturated, where any carbon atoms comprising the bridge may be part of one or more optionally substituted rings.
• rings C and D each independently represent an optionally substituted 5- to 12-membered mono- or polycylic ring that may be saturated, partially unsaturated or aromatic and may optionally contain one or more heteroatoms; each R e is independently selected from the group consisting of hydrogen; a ,n ⁇ ' ( z )m group; or an optionally substituted moiety selected from the group consisting of: C 1-20 aliphatic; C 1-20 heteroaliphatic; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle; a 7- to 14-membered saturated or partially unsaturated polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; an 8- to 14- membered polycyclic heteroaryl ring having 1 -5 heteroatoms independently
• unsaturated monocyclic heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 14-membered saturated or partially unsaturated polycyclic heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; phenyl; or an 8- to 14-membered polycyclic aryl ring; wherein if two R e groups are present on the same position, they may be taken
• each R a and R b is independently a substituent present on phenyl rings where two or more R a groups and/or two or more R b groups may be taken together to form one or more optionally substituted rings.
• R a and R b are independently selected from the group consisting of: a group, halogen, -N0 2 , -CN, -SR y , -S(0)R y , -S(0) 2 R y ,
• 2008376-0144 having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 14-membered saturated or partially unsaturated poly cyclic heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; phenyl; or an 8- to 14-membered poly cyclic aryl ring; where two or more adjacent R a or R b groups can be taken together to form an optionally substituted saturated, partially unsaturated, or aromatic 5- to 12-membered ring containing 0 to 4 heteroatoms; wherein each R y and R 4 is independently as defined above and described in classes and subclasses herein.
• a multidentate ligand system in complexes of formula CI in complexes of formula CI
• Q 1 , Q 2 , Q 3 , Q 3 , Q 4 , Q 5 , Q 6 R a , R b and R e are independently as defined above and
• each R c and R d is independently selected from the group consisting of: a " ⁇ ( z m
• 2008376-0144 (NOV-029-PCT) heteroaryl ring having 1 -5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 14-membered saturated or partially unsaturated poly cyclic heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; phenyl; or an 8- to 14-membered polycyclic aryl ring; where two or more R c or R d groups may be taken together with the carbon atoms to which they are attached and any intervening atoms to form one or more optionally substituted rings; and where when two R c or R d groups are attached to the same carbon atom, they may be taken together with the carbon atom to which they are attached to form a moiety selected from the group consisting of: a 3 - to 8- membered spirocyclic ring, a carbon
• a multidentate ligand system in complexes of formula CI in complexes of formula CI
• Q 1 , Q 2 , Q 3 , Q 3 , Q 4 , Q 5 , Q 6 R a , R b , R c , R d and R e are as defined above and described in classes and subclasses herein.
• R a , R b , R c , R d and R e are independently as defined above and described in classes and subclasses herein;
• R 12 is optionally present, and if present is selected from the group consisting of: a ""( z )m group; or an optionally substituted radical selected from the group consisting of C 1-20 aliphatic; C 1-20 heteroaliphatic; and phenyl.
• At least one activating moiety is tethered to only one phenyl ring of a ligand, as shown in formula I:
• M 1 , M 2 , R 12 , R a , R b , R c , R d , and R e are independently as defined above and described in classes and subclasses herein;
• X 1 and X 2 are each independently an anion or a nucleophile capable of ring opening an epoxide; and where one or more activating moieties " w'(z re present on the indicated phenyl ring in any one or more available positions as valency allows. It will be appreciated that, depending on the metal ion(s) selected and their oxidation state, additional counterion X groups and/or metals may be present.
• one or more X groups may interact with multiple metal centers.
• the following formulae are contemplated by the present invention:
• At least one activating moiety is tethered to two phenyl rings of a ligand, as shown in formula II:
• At least one phenyl ring of a ligand is independently selected from the group consisting of:
• each is independently an activating moiety bonded to any unsubstituted positions of a phenyl ring.
• phenyl rings of a metal complex is independently selected from the group consisting of:
• such ligands exist as a mixture of regioisiomers while in other
• the ligands comprise substantially a single regioisomer:
• At least one of the phenyl rings of a metal complex is independently selected from the group consisting of:
• phenyl rings of a metal complex is independently selected from the group consisting of:
• a metal complex comprises at least one moiety independently selected from the group consisting of:
• a catalyst may have an activating moiety attached to different positions on each of the two rings, and such compounds are specifically encompassed within the scope of the present invention.
• activating moieties can be present on multiple parts of the ligand, for instance activating moieties can be present on the diamine bridge and on one or both phenyl rings in the same catalyst.
• At least one activating moiety is tethered to a diamine bridge of a ligand, as shown in formula Ill-a, Ill-b, and III-c:
• At least one activating moiety is tethered to a diamine bridge of a ligand, as shown in formula IV-a, IV-b, and IV-c:
• each of R a , R b , R c , R d , R e , Z, m, M 1 , M 2 , X 1 , X 2 , and R 12 is independently as defined above and described in classes and subclasses herein.
• at least one activating moiety is tethered to a cyclic diamine bridge of a ligand, as shown in formula V-a, V-b, and V-c:
• R a , R b , R c , R d , R e , Z, m, M 1 , M 2 , X 1 , X 2 , and R 12 is independentlyed above and described in classes and subclasses herein.
• At least one activating moiety is tethered to a cyclic diamine bridge of a ligand, as shown in formula Vl-a, Vl-b, and VI-c:
• provided metal complexes are of formula Vll-a through
• each of X 1 and X 2 if present, is independently as defined above and described in classes and subclasses herein; and each of R c , R d , R e , Z, m, M 1 , and M 2 is independently as defined above and described in classes and subclasses herein.
• metal complexes of the present invention include, but are not limited to those in Table 1 below:
• each M is independently as described above for M 1 or M 2 .
• M 1 and M 2 is Co-X, where X is as defined above and described in classes and subclasses herein.
• M 1 and M 2 is Co-OC(0)CF 3 .
• M 1 and M 2 is Co-OAc.
• M 1 and M 2 is Co-OC(0)C 6 F5.
• M 1 and M 2 is C0-N3.
• M 1 and M 2 is Co-Cl.
• M 1 and M 2 are Co-nitrophenoxy. In certain embodiments, for complexes of Table 1, M 1 and M 2 is Co-dinitrophenoxy. In some embodiments, for complexes of Table 1, M 1 and M 2 is Cr- X.
• the present disclosure provides methods of polymerization comprising contacting an epoxide with carbon dioxide in the presence of a provided metal complex to form a polycarbonate.
• the present invention provides a method of polymerization, the method comprising: a) providing an epoxide of formula: wherein:
• R a is hydrogen or an optionally substituted radical selected from the group
• 2008376-0144 independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10- membered bicyclic heteroaryl ring having 1 -5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and each of R b , R c , and R d is independently hydrogen or an optionally substituted radical selected from the group consisting of C 1-12 aliphatic; C 1-12
• a provided polymer has a formula:
• R b , R c , and R d are each hydrogen.
• R a is optionally substituted C 1-12 aliphatic. In some embodiments, R a is optionally substituted C 1-12 heteroaliphatic . In some embodiments, the epoxide is ethylene oxide, propylene oxide, or cyclohexene oxide.
• one of R a , R b , R c , and R d is hydrogen. In certain embodiments, two of R a , R b , R c , and R d are hydrogen. In certain embodiments, three of R a' , R b' , R c' , and R d' are hydrogen.
• R a is hydrogen. In certain embodiments, R b is hydrogen. In certain embodiments, R c is hydrogen. In certain embodiments, R d is hydrogen.
• R a , R b , R c , and R d are each independently an optionally substituted C 1-30 aliphatic group. In certain embodiments, R a , R b , R c , and R d are each independently an optionally substituted C 1-20 aliphatic group. In certain embodiments, R a' , R b' , R c' , and R d' are each independently an optionally substituted C 1-12 aliphatic group. In certain embodiments, R a , R b , R c , and R d are each independently an optionally substituted C 1-8 aliphatic group. In certain embodiments, R a , R b , R c , and R d are each independently an optionally substituted C 1-30 aliphatic group. In certain embodiments, R a , R b , R c , and R d are each independently an optionally substituted C 1-20 aliphatic group. In certain embodiments, R a'
• R a , R b' , R c' , and R d' are each independently an optionally substituted C 3-12 aliphatic group.
• R a is an optionally substituted C 1-30 aliphatic group.
• R b is an optionally substituted C 1-30 aliphatic group.
• R c is an optionally substituted C 1-30 aliphatic group.
• R d is an optionally substituted Ci-30 aliphatic group.
• an R a and an R b attached to the same carbon are taken together to form one or more optionally substituted 3-12-membered carbocyclic rings. In some embodiments, an R a and an R b attached to the same carbon are taken together to form a polycyclic carbocycle comprising two or more optionally substituted 3-8- membered carbocyclic rings. In some embodiments, an R a and an R b attached to the same carbon are taken together to form a polycyclic carbocycle comprising two or more optionally substituted 5-7-membered carbocyclic rings.
• an R a and an R b attached to the same carbon are taken together to form a bicyclic carbocycle comprising two optionally substituted 3-12- membered carbocyclic rings. In some embodiments, an R a and an R b attached to the same carbon are taken together to form a bicyclic carbocycle comprising two optionally substituted 3-8-membered carbocyclic rings. In some embodiments, an R a and an R b attached to the same carbon are taken together to form a bicyclic carbocycle comprising two optionally substituted 5-7-membered carbocyclic rings.
• an R a and an R b attached to the same carbon are taken together to form an optionally substituted 3-12-membered carbocyclic ring. In certain embodiments, an R a and an R b attached to the same carbon are taken together to form an optionally substituted 3-8-membered carbocyclic ring. In certain embodiments, an R a and an R b attached to the same carbon are taken together to form an optionally substituted 5-7-membered carbocyclic ring.
• an R b and an R c attached to adjacent carbons are taken together to form one or more optionally substituted 3-12-membered carbocyclic rings. In some embodiments, an R b and an R c attached to adjacent carbons are taken together to
• 2008376-0144 form a polycyclic carbocycle comprising two or more optionally substituted 3-8- membered carbocyclic rings.
• an R b and an R c attached to adjacent carbons are taken together to form a polycyclic carbocycle comprising two or more optionally substituted 5-7-membered carbocyclic rings.
• an R b and an R c attached to adjacent carbons are taken together to form a bicyclic carbocycle comprising two optionally substituted 3-12- membered carbocyclic rings.
• an R b and an R c attached to adjacent carbons are taken together to form a bicyclic carbocycle comprising two optionally substituted 3-8-membered carbocyclic rings. In some embodiments, an R b and an R c attached to adjacent carbons are taken together to form a bicyclic carbocycle comprising two optionally substituted 5-7-membered carbocyclic rings.
• an R b and an R c attached to adjacent carbons are taken together to form an optionally substituted 3-12-membered carbocyclic ring. In certain embodiments, an R b and an R c attached to adjacent carbons are taken together to form an optionally substituted 3-8-membered carbocyclic ring. In certain embodiments, an R b and an R c attached to adjacent carbons are taken together to form an optionally substituted 5-7-membered carbocyclic ring.
• the polymer comprises a copolymer of two different repeating units where R a , R b , and R c of the two different repeating units are not all the same.
• a polymer comprises a copolymer of three or more different repeating units wherein R a , R b , and R c of each of the different repeating units are not all the same as R a , R b , and R c of any of the other different repeating units.
• a polymer is a random copolymer.
• a polymer is a tapered copolymer.
• a polymer contains a metal complex as described herein.
• a polymer comprises residue of a metal complex as described herein.
• a polymer comprises a salt of an organic cation and X, wherein X is a nucleophile or counterion.
• X is 2,4- dinitrophenolate anion.
• R a is optionally substituted C 1-12 aliphatic. In some embodiments, R a is optionally substituted C 1-12 heteroaliphatic. In some embodiments, R a is optionally substituted phenyl. In some embodiments, R a is optionally substituted 8- to 10-membered aryl. In some embodiments, R a is optionally substituted 5- to 10- membered heteroaryl. In some embodiments, R a is optionally substituted 3- to 7- membered heterocyclic .
• R a is selected from methyl, ethyl, propyl, butyl, vinyl, allyl, phenyl, trifluoromethy ; 5 or any two or more of the above. In certain embodiments, R a is methyl. In certain embodiments, R a is ethyl. In certain
• R a is propyl. In certain embodiments, R a is butyl. In certain
• R a is vinyl. In certain embodiments, R a is allyl. In certain embodiments, R a is In certain embodiments, R a is trifluoromethyl. In certain embodiments,
• R a is ⁇ v . in certain embodiments, R a is ' v . in certain embodiments,
• R a' is .
• R a is
• R b is hydrogen. In some embodiments, R b is optionally substituted C 1-12 aliphatic. In some embodiments, R b is optionally substituted C 1-12 heteroaliphatic. In some embodiments, R b is optionally substituted phenyl. In some embodiments, R b is optionally substituted 8- to 10-membered aryl. In some embodiments, R b is optionally substituted 5- to 10-membered heteroaryl. In some embodiments, R b is optionally substituted 3- to 7-membered heterocyclic .
• R c is hydrogen. In some embodiments, R c is optionally substituted C 1-12 aliphatic. In some embodiments, R c is optionally substituted C 1-12 heteroaliphatic. In some embodiments, R c is optionally substituted phenyl. In some embodiments, R c is optionally substituted 8- to 10-membered aryl. In some embodiments, R c is optionally substituted 5- to 10-membered heteroaryl. In some embodiments, R c is optionally substituted 3- to 7-membered heterocyclic .
• R a and R c are taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C 3- Ci4 carbocycle, optionally substituted 3- to 14-membered heterocycle, optionally substituted phenyl, optionally substituted Cs-Cio aryl, and optionally substituted 5- to 10- membered heteroaryl.
• R b and R c are taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C 3 _ Ci4 carbocycle, optionally substituted 3- to 14-membered heterocycle, optionally substituted phenyl, optionally substituted Cs-Cio aryl, and optionally substituted 5- to 10- membered heteroaryl.
• R a and R b are taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C 3 _ Ci4 carbocycle, optionally substituted 3- to 14-membered heterocycle, optionally substituted phenyl, optionally substituted Cs-Cio aryl, and optionally substituted 5- to 10- membered heteroaryl.
• the invention includes methods for synthesizing polyethers from epoxides. Suitable methods of performing these reactions are disclosed in US Patent No. 7,399,822, the entire contents of which are hereby incorporated herein by reference. In some embodiments, the invention includes methods for synthesizing cyclic carbonates from carbon dioxide and epoxides using catalysts described above, suitable methods of performing this reaction are disclosed in US Patent No. 6,870,004, which is incorporated herein by reference.

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