WO2001019786A1 - Ligands catalysants, complexes metalliques catalytiques, et procedes d'utilisation et de fabrication associes - Google Patents

Ligands catalysants, complexes metalliques catalytiques, et procedes d'utilisation et de fabrication associes Download PDF

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Publication number
WO2001019786A1
WO2001019786A1 PCT/US1999/021156 US9921156W WO0119786A1 WO 2001019786 A1 WO2001019786 A1 WO 2001019786A1 US 9921156 W US9921156 W US 9921156W WO 0119786 A1 WO0119786 A1 WO 0119786A1
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substituted
aryl
cycloalkyl
alkyl
group
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PCT/US1999/021156
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English (en)
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Anil S. Guram
Cheryl Lund
Howard W. Turner
Tetsuo Uno
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Symyx Technologies
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Priority to EP99974013A priority Critical patent/EP1131283A1/fr
Priority to AU60406/99A priority patent/AU6040699A/en
Priority to PCT/US1999/021156 priority patent/WO2001019786A1/fr
Publication of WO2001019786A1 publication Critical patent/WO2001019786A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
    • C07C211/55—Diphenylamines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C223/00—Compounds containing amino and —CHO groups bound to the same carbon skeleton
    • C07C223/06—Compounds containing amino and —CHO groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/24—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00277—Apparatus
    • B01J2219/00279—Features relating to reactor vessels
    • B01J2219/00306—Reactor vessels in a multiple arrangement
    • B01J2219/00313—Reactor vessels in a multiple arrangement the reactor vessels being formed by arrays of wells in blocks
    • B01J2219/00315—Microtiter plates
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00603—Making arrays on substantially continuous surfaces
    • B01J2219/00659—Two-dimensional arrays
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00718—Type of compounds synthesised
    • B01J2219/0072—Organic compounds
    • B01J2219/00738—Organic catalysts
    • C—CHEMISTRY; METALLURGY
    • C40—COMBINATORIAL TECHNOLOGY
    • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
    • C40B60/00—Apparatus specially adapted for use in combinatorial chemistry or with libraries
    • C40B60/14—Apparatus specially adapted for use in combinatorial chemistry or with libraries for creating libraries

Definitions

  • the present invention relates to new organic compounds (e.g., Hgands), their metal complexes and compositions using those compounds; the invention also relates to the field of catalysis.
  • this invention relates to new compounds which when combined with suitable metals or metal precursor compounds provide useful catalysts for various bond-forming reactions, including polymerizations and small molecule transformations.
  • the invention also relates to combinatorial chemistry in that combinatorial techniques were used in connection with creating the ligands and testing compositions containing the ligands.
  • Ancillary (or spectator) ligand-metal coordination complexes e.g., organometallic complexes
  • compositions are useful as catalysts, additives, stoichiometric reagents, monomers, solid state precursors, therapeutic reagents and drugs.
  • Ancillary ligand-metal coordination complexes of this type can be prepared by combining an ancillary ligand with a suitable metal compound or metal precursor in a suitable solvent at a suitable temperature.
  • the ancillary ligand contains functional groups that bind to the metal center(s), remain associated with the metal center(s), and therefore provide an opportunity to modify the steric, electronic and chemical properties of the active metal center(s) of the complex.
  • Certain known ancillary ligand-metal complexes and compositions are catalysts for reactions such as oxidation, reduction, hydrogenation, hydrosilylation, hydrocyanation, hydroformylation, polymerization. carbonylation, isomerization, metathesis, carbon-hydrogen activation, carbon- halogen activation, cross-coupling. Friedel -Crafts acylation and alkylation, hydration, dimerization, trimerization, oligomerization, Diels-Alder reactions and other transformations. See, e.g., U.S. patents nos. 5,576,460 and 5,550,236, both of which are incorporated herein by reference.
  • ancillary ligand-metal complexes and compositions are in the field of polymerization catalysis.
  • the ancillary ligand offers opportunities to modify the electronic and/or steric environment surrounding an active metal center. This allows the ancillary ligand to create possibly different polymers.
  • Ancillary ligands and ancillary metal complexes that are similar to those disclosed herein have been discussed in WO 98/30609, incorporated herein by reference for all purposes.
  • the invention disclosed herein is a new ligand (1 e , an ancillary ligand), which can be characterized by the general formula
  • each R 1 , R 2 , R , R and R is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof, optionally, R 1 and R 2 are joined together in a ring structure and/or R and R 4 are joined together in a ring structure and/or R 1 and R 6 are joined together in a ring structure, and b is 0, 1 , 2, 3 or 4 Where b is at least 2, two R 6 groups may be joined in a fused ring structure with the benzene ring in the backbone of the ligand G is either oxygen or nitrogen When G is oxygen, a is 0 When G is nitrogen,
  • this invention is a compound characterized by the general formula
  • each R 1 , R 2 , R ⁇ R 4 , R S and R 6 is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof, optionally, R 1 and R 2 are joined together in a ring structure and/or R and R 4 are joined together in a ring structure and/or R 4 and R are joined together in a ring structure and/or R 1 and R 6 are joined together in a ring structure; G is either oxygen or nitrogen and a is either 1 or 2 depending on G; and b is 0, 1, 2, 3 or 4. When G is nitrogen and a is 2, the two R groups may also join to form a ring structure
  • This invention also relates to a novel method of making these new ligands.
  • the general method of making these ligands is to start with a compound characterized by the general formula:
  • R 4 and R are as defined above and X is selected from the group consisting of chloro, bromo, iodo, triflate, tosylate and nonaflate; and R 8 and R 9 are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno. and combinations thereof.
  • This compound is reacted with an amine characterized by the general formula HNR'R 2 , where R 1 and R 2 are as defined above.
  • This provides ligands within the second aspect.
  • an acetyl or ketal functionality of the product is then hydroylzed, providing ligands within the first aspect.
  • the product can be reacted with a primary or secondary amine to transform the ligand. Hydrogenation is thereafter an optional step. All steps may or may not be performed using parallel or high throughput or combinatorial methods.
  • this invention provides new metal-ligand complexes or compositions comprising the new ligands and a metal precursor.
  • the ligands can be included in a composition including a suitable metal or metal precursor compound that can be of the form ML n , where the composition has catalytic properties.
  • the ligands can be coordinated with a metal precursor to form metal-ligand complexes, which may be catalysts.
  • the metal-ligand complexes can be
  • Y characterized by one of many different general formulas depending on how the ligand attaches to or associates with the metal.
  • a further aspect of this invention provides for the novel ligands, compositions or complexes to be created and tested in a combinatorial manner.
  • the ligands, compositions or complexes may be in an array with each ligand, composition or complex in a different region of a substrate.
  • the number of ligands, compositions or complexes on a single substrate will vary according to the desired density, but will typically have at least 10 ligands, compositions or complexes on a single substrate.
  • These metal-ligand complexes or compositions catalyze polymerization and copolymerization reactions, particularly with monomers that are olefins, diolefins or otherwise acetylenically unsaturated.
  • such reactions include carbonylation, hydroformylation, hydroxycarbonylation, hydrocarbonylation, hydroesterification, hydrogenation, transfer hydrogenation, hydrosilylation, hydroboration, hydroamination, epoxidation, aziridation, reductive amination, C-H activation, insertion, C-H activation-insertion, C-H activation-substitution, C-halogen activation, C- halogen activation-substitution, C-halogen activation-insertion, cyclopropanation.
  • a polymerization process is disclosed for olefins, diolefins and other acetylenically unsaturated compounds.
  • the polymerization process involves contacting monomers to the catalyst compositions or to the coordination complexes of this invention under polymerization conditions.
  • the catalyst compositions or the coordination complexes may be active catalysts themselves or make be activated with a known activating technique or compound.
  • the polymerization process can be continuous, batch or semi-batch and can be homogeneous or heterogeneous, as discussed further below.
  • the inventions disclosed herein are new ligands that may be combined with metals or metal precursor compounds to form coordination complexes or compositions of matter, which are useful as catalysts for chemical reactions.
  • the invention also is for processes for making the ligand, processes for making the metal complexes and processes for using the resultant composition or coordination complex as a catalyst.
  • the invention provides these new compounds and compositions and complexes in an array format.
  • R 1 , R 2 , R 3 , R 4 , and R 5 can be identical or different (e.g. R 1 , R 2 , R 3 , R 4 , and R 5 may all be substituted alkyls or R 1 and R 2 may be a substituted alkyl and R 3 may be an aryl, etc.).
  • R group will generally have the structure that is recognized in the art as corresponding to R groups having that name. For the purposes of illustration, representative R groups as enumerated above are defined herein. These definitions are intended to supplement and illustrate, not preclude, the definitions known to those of skill in the art.
  • alkyl is used herein to refer to a branched or unbranched, saturated or unsaturated acyclic hydrocarbon radical. Suitable alkyl radicals include, for example, methyl, ethyl, n-propyl, i-propyl, 2-propeny] (or allyl), vinyl, n-butyl, t-butyl, i-butyl (or 2-methylpropyl), etc. In particular embodiments, alkyls have between 1 and 200 carbon atoms, between 1 and 50 carbon atoms or between 1 and 20 carbon atoms.
  • Substituted alkyl refers to an alkyl as just described in which one or more hydrogen atom to any carbon of the alkyl is replaced by another group such as a halogen, aryl, substituted aryl, cycloalkyl, substituted cycloalkyl, and combinations thereof.
  • Suitable substituted alkyls include, for example, benzyl, trifluoromethyl and the like.
  • heteroalkyl refers to an alkyl as described above in which one
  • heteroalkyl ( or more hydrogen atoms to any carbon of the alkyl is replaced by a heteroatom selected from the group consisting of N, O, P, B, S, Si, Se and Ge.
  • the bond between the carbon atom and the heteroatom may be saturated or unsaturated.
  • heteroaryl, substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl, thio, or seleno is within the scope of the term heteroalkyl.
  • Suitable heteroalkyls include cyano, benzoyl, 2-pyridyl, 2-furyl and the like.
  • cycloalkyl is used herein to refer to a saturated or unsaturated cyclic non-aromatic hydrocarbon radical having a single ring or multiple condensed rings.
  • Suitable cycloalkyl radicals include, for example, cyclopentyl, cyclohexyl, cyclooctenyl, bicyclooctyl, etc.
  • cycloalkyls have between 3 and 200 carbon atoms, between 3 and 50 carbon atoms or between 3 and 20 carbon atoms.
  • Substituted cycloalkyl refers to cycloalkyl as just described including in which one or more hydrogen atom to any carbon of the cycloalkyl is replaced by another group such as a halogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl, thio, seleno and combinations thereof.
  • Suitable substituted cycloalkyl radicals include, for example, 4- dimethylaminocyclohexyl, 4,5-dibromocyclohept-4-enyl, and the like.
  • heterocycloalkyl is used herein to refer to a cycloalkyl radical as described, but in which one or more or all carbon atoms of the saturated or unsaturated cyclic radical are replaced by a heteroatom such as nitrogen, phosphorous, oxygen, sulfur, silicon, germanium, selenium, or boron.
  • Suitable heterocycloalkyls include, for example, piperazinyl, morpholinyl, tetrahydropyranyl, tetrahydrofuranyl, piperidinyl, pyrrolidinyl, oxazolinyl and the like.
  • Substituted heterocycloalkyl refers to heterocycloalkyl as just described including in which one or more hydrogen atom to any atom of the heterocycloalkyl is replaced by another group such as a halogen, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl, thio, seleno and combinations thereof.
  • Suitable substituted heterocycloalkyl radicals include, for example, N-
  • aryl is used herein to refer to an aromatic substituent which may be a single aromatic ring or multiple aromatic rings which are fused together, linked covalently, or linked to a common group such as a methylene or ethylene moiety.
  • the common linking group may also be a carbonyl as in benzophenone or oxygen as in diphenylether or nitrogen in diphenylamine.
  • the aromatic ring(s) may include phenyl, naphthyl, biphenyl, diphenylether, diphenylamine and benzophenone among others.
  • aryls have between 1 and 200 carbon atoms, between 1 and 50 carbon atoms or between 1 and 20 carbon atoms.
  • Substituted aryl refers to aryl as just described in which one or more hydrogen atom to any carbon is replaced by one or more functional groups such as alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, halogen, alkylhalos (e.g., CF ), hydroxy, amino, phosphido, alkoxy, amino, thio and both saturated and unsaturated cyclic hydrocarbons which are fused to the aromatic ring(s), linked covalently or linked to a common group such as a methylene or ethylene moiety.
  • the linking group may also be a carbonyl such as in cyclohexyl phenyl ketone.
  • heteroaryl refers to aromatic rings in which one or more carbon atoms of the aromatic ring(s) are replaced by a heteroatom(s) such as nitrogen, oxygen, boron, selenium, phosphorus, silicon or sulfur.
  • Heteroaryl refers to structures that may be a single aromatic ring, multiple aromatic ring(s), or one or more aromatic rings coupled to one or more non- aromatic ring(s). In structures having multiple rings, the rings can be fused together, linked covalently, or linked to a common group such as a methylene or ethylene moiety.
  • the common linking group may also be a carbonyl as in phenyl pyridyl ketone.
  • heteroaryl refers to heteroaryl as just described including in which one or more hydrogen atoms to any atom of the heteroaryl moiety is replaced by another group such as a halogen, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl, thio, seleno and combinations thereof.
  • Suitable ⁇ substituted heteroaryl radicals include, for example, 4-N,N- dimethylaminopyridine.
  • alkoxy is used herein to refer to the -OZ 1 radical, where Z 1 is selected from the group consisting of alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocylcoalkyl, substituted heterocycloalkyl, silyl groups and combinations thereof as described herein.
  • Suitable alkoxy radicals include, for example, methoxy, ethoxy, benzyloxy, t-butoxy, etc.
  • aryloxy where Z is selected from the group consisting of aryl, substituted aryl, heteroaryl, substituted heteroaryl, and combinations thereof. Examples of suitable aryloxy radicals include phenoxy, substituted phenoxy, 2-pyridinoxy, 8-quinalinoxy and the like.
  • silyl refers to the -SiZ'Z 2 Z 3 radical, where each of Z 1 , Z 2 , and Z ⁇ is independently selected from the group consisting of alkyl, substituted alkyl, cycloalkyl, heterocycloalkyl, heterocyclic, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, amino, silyl and combinations thereof.
  • boryl refers to the -BZ'Z 2 group, where each of Z 1 and 7f is independently selected from the group consisting of alkyl, substituted alkyl, cycloalkyl, heterocycloalkyl, heterocyclic, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, amino, silyl and combinations thereof.
  • phosphino refers to the group -PZ'Z 2 , where each of Z 1 and Z " is independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, cycloalkyl, heterocycloalkyl, heterocyclic, aryl, heteroaryl, silyl, alkoxy, aryloxy, amino and combinations thereof.
  • amino is used herein to refer to the group -NZ'Z " , where each of Z 1 and Z 2 is independently selected from the group consisting of hydrogen; alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl. heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl and combinations thereof.
  • thio is used herein to refer to the group — SZ 1 , where Z 1 is selected from the group consisting of hydrogen; alkyl. substituted alkyl, cycloalkyl, substituted cycloalkyl. heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl and combinations thereof.
  • seleno is used herein to refer to the group -SeZ 1 , where Z 1 is selected from the group consisting of hydrogen; alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl and combinations thereof.
  • saturated refers to lack of double and triple bonds between atoms of a radical group such as ethyl, cyclohexyl, pyrrolidinyl, and the like.
  • unsaturated refers to the presence one or more double and triple bonds between atoms of a radical group such as vinyl, acetylenyl, oxazolinyl, cyclohexenyl, acetyl and the like.
  • each R 1 , R 2 , R 3 , R 4 , R 5 and R is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof; optionally, R 1 and R 2 are joined together in a ring structure and/or R and R 4 are joined together in a ring structure and/or R and R " are joined together in a ring structure; and b is 0, 1, 2, 3 or 4.
  • G is an element selected from the group consisting of oxygen and nitrogen.
  • a is 0 when G is oxygen and a is 1 when G is nitrogen.
  • a is 1 when G is oxygen and a is 2 when G is nitrogen.
  • the two R 3 groups may be the same or different and optionally may be joined together in a ring structure.
  • R and R ⁇ are independently selected from a group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl and silyl.
  • R 1 and R 2 are hydrogen, methyl, ethyl, propyl, butyl, cyclopentyl, cylcohexyl, cyclooctyl, phenyl, naphthyl, benzyl, trimethylsilyl, and the like.
  • the ring including R 1 , R 2 and N
  • R and R" together are ethylene (giving a 3-member ring), propylene (giving a 4-membered ring), butylene
  • R 1 is a substituted or unsubstituted phenyl and R 2 is hydrogen. If R 1 is a substituted phenyl, there may be 1 , 2, 3, 4 or 5 substituents attached to carbon atoms in the phenyl ring. Each of these substituents may be independently selected from the group consisting of alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof.
  • R 3 is selected from a group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl.
  • heterocycloalkyl substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkyloxy, aryloxy, amino, silyl, boryl and phosphino.
  • R 3 are methyl, ethyl, propyl, butyl, cyclohexyl, cyclopropyl, cycloheptyl, t-butyl, phenyl, biphenyl, naphthyl, benzyl, pyridyl, furyl, quinolyl, morpholiny], cyano, methoxy, ethoxy, t-butoxy, phenoxy.
  • benzyloxy dimethylamino, diethylamino, diphenylamino, phenylmethylamino, benzylmethylamino, trimethylsilyl, dimethyl-t-butylsilyl, triphenylsilyl, triethoxysilyl, dimethylboryl, diphenylboryl, diphenoxyboryl, 1 ,2-
  • R is benzyl or a substituted or unsubstituted phenyl
  • R 3 is a substituted phenyl and there are 1 , 2, 3, 4 or 5 substituents on the phenyl ring, with each of said substituents independently selected from the group consisting of alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl.
  • substituted heterocycloalkyl aryl, substituted aryl, heteroaryl, substituted heteroaryl, hydroxy, halogens, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof
  • substituents on the substituted phenyl are selected from the group consisting of chloro, fluoro, lodo, bromo, methyl, ethyl, propyl, butyl, cyclopentyl, cylcohexyl, cyclooctyl, phenyl, naphthyl, benzyl, trimethylsilyl and isomers thereof
  • R 4 is selected from the group consisting of hydrogen, alkyl, substituted alkyl, heteroalkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkyloxy, aryloxy, boryl, amino and silyl
  • R 4 may be selected from the group consisting of hydrogen, alkyl, aryl and cycloalkyl
  • R 4 are hydrogen, methyl, ethyl, propyl, butyl, cyclopentyl, cylcohexyl, cyclooctyl, phenyl, naphthyl, benzyl, pyridyl, furyl, morpho no, methoxy, ethoxy, butoxy, phenoxy, benzyloxy, dimethylboryl, diphenylboryl,
  • the ring (including R , R , G and C) has from 4 to 15 non-hydrogen atoms as part of the backbone of the ring
  • G is nitrogen and a is 1 and R is selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino and combinations thereof
  • R and R 4 together are ethylene (giving a 4-membered ring), butylene (giving a 6-membered ring), bicyclooctyl, bicyclohexyl, 2,2'-biphenyl (giving a dibenzo fused 6-membered
  • R 6 is selected from the group consisting of electron withdrawing and electron donating groups and b is 0, 1 , 2, 3 or 4.
  • R 6 can take any open position on the benzene ring that helps form the backbone of the ligand. More specifically, R may be chosen from the group consisting of alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl. heteroaryl, substituted heteroaryl, silyl, amino, alkoxy, aryloxy, phosphino, boryl, transition metals, halogens and combinations thereof.
  • R 6 examples include methyl, ethyl, propyl, t-butyl, phenyl, cyano, acetyl, benzyl, nitro, dimethylamino, diethylamino, methylphenylamino, benzylmethylamino, trimethylsilyl, dimethylboryl, diphenylboryl, methylphenylboryl, dimethoxyboryl, chromium tricarbonyl, ruthenium tricarbonyl, and cyclopentadienyl iron.
  • two or more R groups combine to form a fused ring structure with the aromatic group that forms a part of the ligand backbone.
  • the additional fused ring may or may not contain a heteroatom.
  • the aromatic group that is part of the backbone as combined with two or more R 6 groups that have formed a fused ring are naphthalene, quinoline, indole and the like.
  • R 5 may be selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl. substituted cycloalkyl. heteroalkyl, aryl, substitute aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, amino and silyl.
  • R 5 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, cyclopentyl, cylcohexyl, cyclooctyl, phenyl, naphthyl, benzyl, pyridyl, furyl, morpholino, methoxy, ethoxy, butoxy, phenoxy, benzyloxy, dimethylboryl.
  • R 5 may be joined in a ring structure with G and R 3 in the backbone of the ring.
  • R 4 and R s are joined in a ring structure, having at least three atoms in the backbone
  • the ring (including R 4 , R and C) has from 3 to 15 non-hydrogen atoms as part of the backbone of the ring.
  • R 4 and R s together are ethylene (giving a 3-member ring), propylene (giving a 4-membered ring), butylene
  • the ligands of this invention may be synthesized using an aryl animation reaction.
  • the synthesis can be carried out in solution phase or solid phase (using organic or inorganic supports).
  • the hgands may be left on the support and used with metal added metal complexes as heterogeneous catalysts.
  • the ligands can be cleaved either before or after reaction with a metal precursor and then used as a homogeneous catalyst.
  • scheme 1 One the general route for synthesis of the ligands of this invention is shown below in scheme 1 :
  • step 1 is an aryl amination reaction starting with a compound characterized by the general formula:
  • R 4 and R are as defined above and X is selected from the group consisting of chloro, bromo, iodo, triflate, nonaflate, alkyl sulfonates, aryl sulfonates and tosylate; and R and R are independently selected from the group consisting of alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof.
  • variable groups have the previously indicated meanings.
  • Step 1 is any scheme is the aryl amination reaction.
  • This reaction uses an amine that can be characterized by the general formula HNR'R 2 , where R 1 and R 2 are as defined above.
  • This aryl amination reaction is typically performed using a catalyst that comprises known or possibly new metal and ligand catalyst compositions.
  • the catalyst may be characterized by the general formula M7L', where M' is a complex that contains a metal selected from the group consisting of late transition metals, preferably a Group 10 metal such as Pd, Ni or Pt.
  • M' is any homogeneous or heterogeneous metal precursor catalyst or catalyst
  • L' is a ligand that may be selected from the group consisting of phosphine or nitrogen ligands.
  • L' may be monodentate, bidentate, tridentate, hemi-labile, unsubstituted or substituted, supported or unsupported, water- soluble or insoluble, soluble or insoluble in organic solvents including fluorinated solvents.
  • the reaction can take place at known conditions, such as a temperature of from room temperature to about 150°C.
  • Aryl amination reactions are described in U.S. Patent No. 5,576,460 herein incorporated by reference.
  • the second step of the reaction converts compound 2 to compound 3 by hydrolysis of an acetal or ketal functionality. This reaction can be performed by one of skill in the art. See, e.g., Greene, Theodra W. and Wuts, Peter G.M., Protecting Groups in Organic Synthesis, 2 nd ft Edition (John Wiley & Sons, New York, New York 1991), herein incorporated by reference
  • compound 3 can be reacted with a primary or secondary amine for transform the ligand
  • the primary or secondary amine in step 3 or 3' can be characterized by the general formula H a NR a , where R 3 is as defined above and a is 1 for a primary amine and a is 2 for a secondary amine
  • a primary amine provides compound 4 in above scheme 1 following step 3
  • a secondary amine in the presence of a hydride source provides a compound within above general ligand structure II in above scheme 1 following step 3' If a primary amine is employed, hydrogenation is thereafter an optional fourth step in scheme 1
  • the ligands of this invention will be combined with such a metal compound or precursor and the product of such combination is not determined, if a product forms
  • the ligand may be added to a reaction vessel at the same time as the metal or metal precursor compound along with the reactants
  • the metal precursor compounds may be characterized by the general formula M(L) n where M is a metal selected from the group consisting of Groups 3, 4, 5, 6, 7, 8, 9 and 10 of the Periodic Table of Elements
  • M is selected from the group consisting of Ti, Zr, Hf, V, Ta, Cr, W, Mo, Ru, Co, Ni, Pd, Fe, Mn
  • Pt L is a ligand chosen from the group consisting of hahde, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycl
  • each A is independently selected from a group consisting of alkyl, substituted alkyl, heteroalkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, and amino.
  • the ligand to metal precursor compound ratio is in the range of about 0.01 : 1 to about 100: 1 , more preferably in the range of about 0.5: 1 to about 20: 1.
  • the ligand will be mixed with a suitable metal precursor compound prior to or simultaneous with allowing the mixture to be contacted to the reactants.
  • a metal-ligand complex may be formed, which may be a catalyst.
  • the metal complexes may be characterized by any of the following general formulas.
  • the possible metal complexes formed include:
  • the possible metal complexes formed include:
  • each R , R ⁇ , R , R , R , R , G, a and b are as defined above;
  • M is a transition metal selected from the group consisting of Groups 3, 4, 5, 6, 7, 8, 9 and 10 of the Periodic Table of Elements. Selection of the metal is most preferably dependent on whether the ligand is monoanionic or dianionic. In more specific embodiments, M is selected from the group consisting of V, Ta, Cr, W, Mo, Ru, Co, Ni, Pd, Fe. Mn and Pt.
  • L is independently each occurrence, a neutral and/or charged ligand.
  • L is a ligand chosen from the group consisting of halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl, silyl, hydrido, thio, seleno, phosphino, amino, and combinations thereof.
  • L is selected from the group consisting of hydrogen, halogens, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof.
  • L is selected from the group consisting of carbon monoxide, isocyanide, nitrous oxide, PA 3 , NA 3 , OA 2 , SA 2 , SeA 2 , and combinations thereof, wherein each A is independently selected from a group consisting of alkyl, substituted alkyl, heteroalkyl, cycloalkyl, substituted cycloalkyl. heterocycloalkyl, i substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, and amino.
  • n is the number 0, 1 , 2, 3, 4, and 5. Additionally, m is 1 , 2, 3, or 4.
  • M can be neutral, cationic or anionic.
  • the ligands of this invention that bind to a metal via the N atoms with dative bonds are shown with arrows and covalent binding is shown with a line.
  • Coordination modes described above may or may not depend on the nature of ligands L on the metal M, and for a given ligand L, the coordination modes may switch from one to another at different stages of a catalytic cycle.
  • such reactions include carbonylation, hydroformylation, hydroxycarbonylation, hydrocarbonylation, hydroesterification, hydrogenation, hydrosilylation, hydroboration, hydroamination, epoxidation, aziridation, reductive amination, C-H activation, insertion, C-H activation-insertion, C-H activation-substitution, C-halogen activation, C-halogen activation-substitution, C-halogen activation-insertion, alkene metathesis, polymerization, alkene oligomerization, alkene polymerization, alkyne oligomerization, alkyne polymerization, co- polymerization, CO-alkene co-oligomerization, CO-alkene co-polymerization, CO-alkyne co-oligomerization and CO-alkyne co-polymerization.
  • these reactions may occur at previously known conditions (or possibly novel conditions). Moreover, these reactions may be homogeneous or heterogeneous. In the case of heterogeneous reactions, the ligands may be supported, with or without the metal coordinated, on an organic or inorganic support. Suitable supports include silicas, aluminas, zeolites, polyethyleneglycols, polystyrenes, polyesters, polyamides, peptides and the like.
  • the complexes and compositions of this invention are active catalysts also for the polymerization of olefins, possibly in combination with an activator or activating technique.
  • an activator or activating technique those of skill in the art may use alumoxanes, strong Lewis acids, compatible noninterfering activators and combinations of the foregoing.
  • the foregoing activators have been taught for use with different metal complexes in the following references, which are hereby incorporated by reference in their entirety: U.S. Patents 5,599,761 , 5,616,664, 5,453,410, 5,153,157, 5,064,802, and EP-A-277,004.
  • Preferred activators include methylalumoxane, trimethylaluminum, AgBF 4 , AgBPh 4 , NaBAr' 4 , H(OEt 2 ) 2 BAr' 4 and the like (where Ar' is a substituted aromatic, like perfluorophenyl or 3,5-(CF ) 2 (C 6 H 3 )).
  • Ratios of neutral complex to activator are on the order of 1 to 1000 to 1000 to 1.
  • a scavenger can also be used with this invention. Scavengers useful herein include metal complexes, alumoxanes, aluminum alkyls and the like. Other additives that are standard for polymerization reactions can be used.
  • the catalysts herein may be used to polymerize ethylenically or acetylenically unsaturated monomers having from 2 to 20 carbon atoms either alone or in combination.
  • Monomers include C 2 to C o • -olefins such as ethylene, propylene, 1-butene, 1-hexene, 1-octene. 4-mtheyl-l-pentene, styrene and mixtures thereof.
  • the compounds and catalysts of this invention usefully polymerize functionalized monomers, such as acetates and acrylates.
  • Novel polymers, copolymers or interpolymers may be formed having unique physical and/or melt flow properties.
  • Such novel polymers can be employed alone or with other polymers in a blend to form products that may be molded, cast, extruded or spun.
  • End uses for the polymers made with the catalysts of this invention include films for packaging, trash bags, foams, coatings, insulating devices and household items.
  • functionalized polymers are useful as solid supports for organometallic or chemical synthesis processes.
  • Polymerization can be carried out in the Ziegler-Natta or Kaminsky-Sinn methodology, including temperatures of from 0°C to 400°C and pressures from atmospheric to 3000 atmospheres.
  • Suspension, solution, slurry, gas phase or high-pressure polymerization processes may be employed with the catalysts and compounds of this invention. Such processes can be run in a batch or continuous mode. Examples of such processes are well known in the art.
  • a support for the catalyst may be employed, which may be alumina, silica or a polymers support. Methods for the preparation of supported catalysts are known in the art. Slurry, suspension, solution and high-pressure processes use a
  • the ligands, metal complexes and compositions of this invention can be prepared and tested for catalytic activity in one or more of the above reactions in a combinatorial fashion.
  • Combinatorial chemistry generally involves the parallel or rapid serial synthesis and/or screening or characterization of compounds and compositions of matter.
  • U.S. Patent No. 5,776,359 and WO 98/03521 both of which are incorporated herein by reference generally disclose combinatorial methods.
  • the ligands, complexes or compositions may be prepared and/or tested in rapid serial and/or parallel fashion, e.g., in an array format.
  • the ligands may be take the form of an array comprising a plurality of compounds wherein each compound can be characterized by either of the general formulas:
  • each R 1 , R 2 , R 3 , R 4 R 5 and R 6 is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof; optionally, R 1 and R 2 are joined together in a ring structure and/or R and R 4 are joined together in a ring structure; G is either oxygen or nitrogen.
  • a is 0 or 1 depending on G.
  • a is 1 or 2 depending on G.
  • b is 0, 1, 2, 3 or 4.
  • each of the plurality of compounds has a different composition and each compound is at a selected region on a substrate such that each compound is isolated from the other compounds.
  • This isolation can take many forms, typically depending on the substrate used. If a flat substrate is used, there may simply be sufficient space between regions so that there cannot be interdiffusion between compounds.
  • the substrate can be a microtiter or similar plate having wells so that each compound is in a region separated from other compounds in other regions by a physical barrier.
  • the array typically comprises at least 10 compounds, complexes or compositions each having a different chemical formula, meaning that there must be at least one different atom or bond differentiating the plurality in the array.
  • each compound, complex or composition is not pure.
  • plurality of compounds are at least 50% pure within said regions.
  • the catalytic performance (activity and selectivity) of the ligands of this invention in combination with a suitable metal precursor or metal-ligand coordination complexes of this invention can be tested in a combinatorial or high throughput fashion.
  • thin layer chromatography (TLC) in combination with imaging technology may be employed.
  • TLC is well known in the art, see for example Vol. 1 , Thin-Layer Chromatography, Reagents & Detection Methods, Jork et al. (VCH Publishers, New York, New York 1990). Polymerizations can also be performed in a combinatorial fashion, see, e.g., commonly owned provisional U.S. Patent Application No. 60/096,603, filed August 13, 1998 (having attorney docket no. 65304-010), herein incorporated by reference. High throughput screening can also be performed optically and in parallel, for example, as disclosed in commonly owned U.S. Patent Applications 09/067,448, filed April 2, 1998, 08/947.085, filed October 8, 1997, and 08/946,135, filed October 7, 1997, each of which is incorporated by reference.
  • Example 1 2-Bromo-l-(dimethoxymethyl)benzene (la). To a 500 mL round bottom flask equipped with a reflux condenser were added 2- bromobenzaldehyde (102. 5 g, 0.554 mol, Aldrich). trimethyl orthoformate (64.9 mL, 0.594 mol, Aldrich), 10-camphor sulfonic acid (1.25 g, 5.40 mmol, Aldrich), and methanol (100 mL). The reaction was heated at reflux for 14 hrs and concentrated in vacuo. The residue was taken up in 500 mL of ether, washed with 200 mL each of sat. aqueous sodium bicarbonate, water, and sat.
  • 2- bromobenzaldehyde 102. 5 g, 0.554 mol, Aldrich
  • trimethyl orthoformate 64.9 mL, 0.594 mol, Aldrich
  • 10-camphor sulfonic acid (1.25
  • Example 3 2-2'(2-Chloro-6-methylanilinophenyl)]-2-methyl-l,3-dioxolane (2b-2): Compound 2b-2 (381 mg, 96 % yield) was obtained as a colorless solid from the reaction of 2-(2'-bromophenyl)-2-methyl- l ,3-dioxolane (318 mg, 1.31 mmol), 2-chloro-6-methylaniline(195 mg, 1.38 mmol), NaO'Bu ( 152 mg, 1.58 mmol), Pd(dba) 2 (15 mg, 0.03 mmol), ligand A ( 18 mg, 0.05 mmol) in toluene (4 mL) at 105 °C for 2 hours.
  • Example 4 2-[2'(2-Isopropylanilinophenyl)]-l,3-dioxolane (2b-3): Compound 2b-3 (354 mg, 90 % yield) was obtained as a yellow oil from the reaction of 2-(2'-bromophenyl)-l ,3-dioxolane (321 mg, 1.40 mmol), 2- isopropylaniline (199 mg, 1.47 mmol), NaO'Bu ( 141 mg, 1.47 mmol), Pd(dba) 2 (16 mg, 0.03 mmol), ligand A (27 mg, 0.08 mmol) in toluene (4 mL) at 105 °C for 75 minutes.
  • Example 5 2-[(2',4',6'-trimethylphenyl)amino]benzaIdehyde (3a-l).
  • sodium t-butoxide 5.77 g, 60.0 mmol, Aldrich
  • Pd(dba) 2 0.144 g, 0.250 mmol, ACROS
  • ligand A 0.174 g, 0.500 mmol
  • la 14.45 g, 62.6 mmol
  • Toluene (130 mL, anhydrous, Aldrich) and 2,4,6- trimethylaniline (8.71 g, 64.4 mmol, Aldrich) were added and the reaction was heated to 105 C for 6 hrs.
  • Example 6 2-[2',6'-(diisopropylphenyl)amino]benzaldehyde (3a-2).
  • sodium t-butoxide (2.88 g, 30.0 mmol, Aldrich)
  • Pd(dba) 2 72 mg, 0.13 mmol, ACROS
  • ligand A 87 mg, 0.25 mmol
  • the crude material was subjected to hydrolysis in the similar way as 3a-l ( THF (50 mL), water (25 mL), and acetic acid (25 mL) at 22 C for 1 hr).
  • the crude product was purified by flash chromatography on a 7x20 cm silica gel column (2.5% ether in hexanes), affording 6.68 g of a very yellow viscous oil (96 %).
  • IR (liquid film) 3292, 1660 cm '1 .
  • Example 7 This example is a general procedure for the formation of 2- mesitylaminobenzaldehyde imines: To a solution of 2- mesitylaminobenzaldehyde 3a-l (957 mg, 4 mmol) in dichloroethane (6 mL) was added benzylamine (429 mg, 4 mmol) via syringe, followed by a catalytic amount of p-toluenesulfonic acid monohydrate (18 mg, ⁇ 1 %) and 4A molecular sieves. The reaction was heated to reflux overnight while stirring under argon. The disappearance of the aldehyde and formation of the imine was followed by GC/MS.
  • Example 8 This example is a general procedure for the formation of 2-(2,6- diisopropylphenyl)aminobenzaldehyde imines.
  • 2-[(2,6- diisopropylphenyl) aminojbenzaldehyde 3a-2 (126 mg, 0.45 mmol) in dichloroethane (500 ⁇ L) was added 2,6-diisopropylaniline (84 ⁇ L, 0.45 mmol) via syringe, followed by a catalytic amount of p-toluenesulfonic acid monohydrate ( 10 mg, 10%).
  • the resulting solution was concentrated and the resulting oil was heated overnight (external temperature 120 °C).
  • Example 9 This example is a general procedure for the formation of 2- mesitylaminobenzaldehyde 2-aminomethylenes. To 4a-2 (0.17 mmol, 60 mg) in dichloroethane (2 mL) was added acetic acid (60 ⁇ L) followed by NaBH(OAc) 3 (0.34 mmol, 70 mg). The resulting mixture was shaken at room temperature for 2 hours. The crude product was extracted from an aqueous Na 2 C0 3 solution with dichloroethane (3 x 2 mL) then passed through a plug of silica gel and concentrated to afford a pale yellow oil.

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Abstract

Selon l'invention, un nouveau ligand présentant un squelette constitué d'un noyau benzénique, peut être combiné avec un composé métallique ou son précurseur, ou formé en un complexe métal-ligand pouvant catalyser un grand nombre de différentes transformations chimiques, y compris des polymérisations oléfiniques. Ces ligands, ces complexes formés à partir de ces ligands, et ces compositions renfermant ces ligands sont utilisés comme catalyseurs, selon la réaction.
PCT/US1999/021156 1999-09-10 1999-09-10 Ligands catalysants, complexes metalliques catalytiques, et procedes d'utilisation et de fabrication associes WO2001019786A1 (fr)

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US9139699B2 (en) 2012-10-04 2015-09-22 Dow Corning Corporation Metal containing condensation reaction catalysts, methods for preparing the catalysts, and compositions containing the catalysts
US9156948B2 (en) 2011-10-04 2015-10-13 Dow Corning Corporation Iron(II) containing complex and condensation reaction catalysts, methods for preparing the catalysts, and compositions containing the catalysts
US9221041B2 (en) 2011-09-20 2015-12-29 Dow Corning Corporation Iridium containing hydrosilylation catalysts and compositions containing the catalysts
US9228061B2 (en) 2011-09-07 2016-01-05 Dow Corning Corporation Zirconium containing complex and condensation reaction catalysts, methods for preparing the catalysts, and compositions containing the catalysts
US9371422B2 (en) 2011-09-07 2016-06-21 Dow Corning Corporation Titanium containing complex and condensation reaction catalysts, methods for preparing the catalysts, and compositions containing the catalysts
US9480977B2 (en) 2011-09-20 2016-11-01 Dow Corning Corporation Ruthenium containing hydrosilylation catalysts and compositions containing the catalysts
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US9480977B2 (en) 2011-09-20 2016-11-01 Dow Corning Corporation Ruthenium containing hydrosilylation catalysts and compositions containing the catalysts
US9545624B2 (en) 2011-09-20 2017-01-17 Dow Corning Corporation Nickel containing hydrosilylation catalysts and compositions containing the catalysts
US9156948B2 (en) 2011-10-04 2015-10-13 Dow Corning Corporation Iron(II) containing complex and condensation reaction catalysts, methods for preparing the catalysts, and compositions containing the catalysts
US9328205B2 (en) 2011-10-04 2016-05-03 Dow Corning Corporation Iron(III) containing complex and condensation reaction catalysts, methods for preparing the catalysts, and compositions containing the catalysts
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