# US 8,772,520 B2 · Preparation of a metal complex

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- Number: US 8,772,520 B2
- Document ID: US8772520B2
- Status: Granted
- Kind: B2
- Application number: 13/318,970
- Filed: 2010-01-12
- Published: 2012-05-10
- Granted: 2014-07-08
- Earliest claimed: 2009-05-06
- Assignees: Johnson Matthey Public Limited Company
- Applicants: Thomas John Colacot; Gabriela Alexandra Grasa; Hongbo Li
- Inventors: Thomas John Colacot; Gabriela Alexandra Grasa; Hongbo Li
- Web page: https://patentgrep.com/patent/US8772520B2

## CPC

- C07F 15/0066: {without a metal-carbon linkage}
- C07F 15/006: {Palladium compounds}
- C07F 17/02: of metals of Groups 8, 9 or 10 of the Periodic Table
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)

## Abstract

The present invention provides a process for the preparation of a Pd(0)Ln complex, where L is a ligand and n is 2, 3 or 4, comprising the steps of: (a) reacting a Pd(II) complex in at least one solvent with a base and ligand L; and (b) if required, adding further base, optionally in at least one solvent, to form the Pd(0)Ln complex; wherein the at least one solvents in steps a and b are independently the same or different, and provided that when n=2, the Pd(II) complex is not bis[tri(ortho-tolyl)phosphine] palladium chloride. The invention also provides novel Pd(0)L2 and Pd(II) complexes.

## Claims

### Claim 1

A process for the preparation of a Pd(0)Ln complex, where L is a ligand and n is 2, comprising the steps of:
a. reacting a Pd(II) complex in at least one solvent with a base and a ligand L; and
b. if required, adding further base, optionally in at least one solvent, to form the Pd(0)Ln complex;
wherein the at least one solvents in steps a and b are independently the same or different; and
wherein the Pd(II) complex is selected from the group consisting of Pd(olefin)x(Hal)2, Pd(Hal)2 and M2Pd(Hal)4, in which each Hal is independently a halide, M is a cation, x is 1 or 2, and wherein when x=1 the olefin is a diolefin and when x=2 the olefin is a mono-olefin.

### Claim 2 (depends on 1)

The process according to claim 1, wherein the Pd(II) complex is Pd(olefin)x(Hal)2.

### Claim 3 (depends on 1)

The process according to claim 1, wherein in step a, ligand L is added to a reaction mixture of the Pd(II) complex in at least one solvent and the base.

### Claim 4 (depends on 1)

The process according to claim 1, wherein in step a, the base is added to a reaction mixture of the Pd(II) complex in at least one solvent and the ligand L.

### Claim 5 (depends on 1)

The process according to claim 1, wherein the base is a hydroxide, alkoxide, carbonate, phosphate or acetate.

### Claim 6 (depends on 1)

The process according to claim 1, wherein the at least one solvents in steps a and b are independently selected from the group consisting of protic solvents, aprotic solvents and combinations thereof.

### Claim 7 (depends on 1)

The process according to claim 1, wherein ligand L is a phosphorus ligand.

### Claim 8 (depends on 7)

The process according to claim 7, wherein the phosphorus ligand is chiral or achiral, monodentate or bidentate phosphorus ligand in which each phosphorus atom is covalently bonded to either 3 carbon atoms or to z heteroatoms and 3-z carbon atoms, where z =1, 2 or 3.

### Claim 9 (depends on 8)

The process according to claim 8, wherein the heteroatom is selected from the group consisting of N and O.

### Claim 10 (depends on 1)

The process according to claim 1, wherein ligand L is a phosphine selected from the group consisting of phenyl-di-t-butylphosphine, di-tert-butyl-neopentylphosphine, 1,2,3,4,5-pentaphenyl-1′-(di-t-butylphosphino)ferrocene, triphenylphosphine, tricyclohexyl phosphine, tri(tert-butyl)phosphine, tris(p-tolyl)phosphine, tris(o-tolyl)phosphine, tris(p-methoxyphenyl)phosphine, tris(p-trifluoromethylphenyl) phosphine, tris(2,4,6-trimethoxyphenyl)phosphine, tris(2,4,6,-trimethyl)phosphine, tris(2,6-dimethylphenyl)phosphine, 1-adamantyl-di-t-butylphosphine, benzyldi-1-adamantylphosphine, butyldi-1-adamantylphosphine, cyclohexyldi-t-butylphosphine, cyclohexyldiphenylphosphine, 2-di-t-butylphosphino-1,1′-binaphthyl, 2-(di-t-butylphosphino)biphenyl, 2-di-t-butylphosphino-2′-(N,N-dimethylamino)biphenyl, 2-di-t-butylphosphino-2′-methylbiphenyl, 2-di-t-butylphosphino-2′,4′,6′-tri-i-propyl-1,1′-biphenyl, 2-di-t-butylphosphino-3,4,5,6 -tetramethyl-2′,4′,6′-tri-i-propylbiphenyl, 2-(dicyclohexylphosphino) biphenyl, 2-(dicyclohexylphosphino)-2′,6′-dimethoxy-1,1′-biphenyl, 2-di-t-cyclohexyl phosphino-2′-(N, N-dimethylamino)biphenyl, 2-di-t-cyclohexylphosphino-2′,6′-di-i-propoxy-1,1′-biphenyl, 2-(dicyclohexylphosphino)-2′,4′,6′-tri-i-propyl-1,1′-biphenyl, 2-di-cyclohexyl phosphino-2′-methylbiphenyl, 2-diphenylphosphino-2′-(N, N-dimethylamino)biphenyl, (4-dimethyl-aminophenyl)(tert-butyl)2phosphine, 1,2-bis(di-tertbutylphosphinomethyl) benzene, 1,3-bis(di-tertbutylphosphinomethyl)propane, 1,2-bis(di-phenylphosphino methyl)benzene, 1,2-bis(di-phenylphosphino)ethane, 1,2-bis(diphenylphosphino) propane, 1,2-bis(di-phenyl phosphino)butane, 1,1′-bis(di-phenylphosphino)ferrocene, N-(2-methoxyphenyl)-2-(di-t-butylphosphino)pyrrole, 1-(2-methoxyphenyl)-2-(di-cyclohexylphosphino)pyrrole, N-phenyl-2-(di-t-butylphosphino)indol, N-phenyl-2-(di-t-butylphosphino)pyrrole, N-phenyl-2-(dicyclohexylphosphino)indol, N-phenyl-2-(di-cyclohexylphosphino)pyrrole and 1-(2,4,6-trimethylphenyl)-2(dicyclohexylphosphino)imidazole.

### Claim 11 (depends on 1)

The process according to claim 1, wherein the Pd(0)Ln complex is selected from the group consisting of:
a. [t-Bu2PhP]2Pd;
b. [t-Bu2(p-PhMe2N)P]2Pd;
c. [Cy3P]2Pd;
d. [t-Bu3P]2Pd;
e. [P(C5H4FeC5Ph5)(t-Bu)2]2Pd;
f. [(o-tol)3P]2Pd; and
g. [t-Bu2(neopentyl)P]2Pd.

### Claim 12

A process for the preparation of a Pd(0)Ln complex, where L is a ligand and n is 3 or 4, comprising the steps of:
a. reacting a Pd(II) complex in at least one solvent with a base and a ligand L; and
b. if required, adding further base, optionally in at least one solvent, to form the Pd(0)Ln complex;
wherein the at least one solvents in steps a and b are independently the same or different.

### Claim 13 (depends on 12)

The process according to claim 12, wherein n is 4.

### Claim 14 (depends on 12)

The process according to claim 12, wherein in step a, ligand L is added to a reaction mixture of the Pd(II) complex in at least one solvent and the base.

### Claim 15 (depends on 12)

The process according to claim 12, wherein in step a, the base is added to a reaction mixture of the Pd(II) complex in at least one solvent and the ligand L.

### Claim 16 (depends on 12)

The process according to claim 12, wherein the Pd(II) complex is selected from the group consisting of Pd(olefin)x(Hal)2, Pd(Hal)2, Pd(phosphine)y(Hal)2 and M2Pd(Hal)4, in which each Hal is independently a halide, M is a cation, and x and y are independently 1 or 2, and wherein when x =1 the olefin is a diolefin, when x =2 the olefin is a mono-olefin, when y =1 the phosphine is a bidentate phosphine, and
when y =2 the phosphine is a monophosphine.

### Claim 17 (depends on 12)

The process according to claim 12, wherein the base is a hydroxide, alkoxide, carbonate, phosphate or acetate.

### Claim 18 (depends on 12)

The process according to claim 12, wherein the at least one solvents in steps a and b are independently selected from the group consisting of protic solvents, aprotic solvents and combinations thereof.

### Claim 19 (depends on 12)

The process according to claim 12, wherein ligand L is a phosphorus ligand.

### Claim 20 (depends on 19)

The process according to claim 19, wherein the phosphorus ligand is chiral or achiral, monodentate or bidentate phosphorus ligand in which each phosphorus atom is covalently bonded to either 3 carbon atoms or to z heteroatoms and 3-z carbon atoms, where z =1, 2 or 3.

### Claim 21 (depends on 20)

The process according to claim 20, wherein the heteroatom is selected from the group consisting of N and O.

### Claim 22 (depends on 12)

The process according to claim 12, wherein ligand L is a phosphine selected from the group consisting of phenyl-di-t-butylphosphine, di-tert-butyl-neopentylphosphine, 1,2,3,4,5-pentaphenyl-1′-(di-t-butylphosphino)ferrocene, triphenylphosphine, tricyclohexyl phosphine, tri(tert-butyl)phosphine, tris(p-tolyl)phosphine, tris(o-tolyl)phosphine, tris(p-methoxyphenyl)phosphine, tris(p-trifluoromethylphenyl) phosphine, tris(2,4,6-trimethoxyphenyl)phosphine, tris(2,4,6,-trimethyl)phosphine, tris(2,6-dimethylphenyl)phosphine, 1-adamantyl-di-t-butylphosphine, benzyldi-1-adamantylphosphine, butyldi-1-adamantylphosphine, cyclohexyldi-t-butylphosphine, cyclohexyldiphenylphosphine, 2-di-t-butylphosphino-1,1′-binaphthyl, 2-(di-t-butylphosphino)biphenyl, 2-di-t-butylphosphino-2′-(N,N-dimethylamino)biphenyl, 2-di-t-butylphosphino-2′-methylbiphenyl, 2-di-t-butylphosphino-2′,4′,6′-tri-i-propyl-1,1′-biphenyl, 2-di-t-butylphosphino-3,4,5,6-tetramethyl-2′,4′,6′-tri-i-propylbiphenyl, 2-(dicyclohexylphosphino) biphenyl, 2-(dicyclohexylphosphino)-2′,6′-dimethoxy-1,1′-biphenyl, 2-di-t-cyclohexyl phosphino-2′-(N, N-dimethylamino)biphenyl, 2-di-t-cyclohexylphosphino-2′,6′-di-i-propoxy-1,1′-biphenyl, 2-(dicyclohexylphosphino)-2′,4′,6′-tri-i-propyl-1,1′-biphenyl, 2-di-cyclohexyl phosphino-2′-methylbiphenyl, 2-diphenylphosphino-2′-(N, N-dimethylamino)biphenyl, (4-dimethyl-aminophenyl)(tert-butyl)2phosphine, 1,2-bis(di-tertbutylphosphinomethyl) benzene, 1,3-bis(di-tertbutylphosphinomethyl)propane, 1,2-bis(di-phenylphosphino methyl)benzene, 1,2-bis(di-phenylphosphino)ethane, 1,2-bis(diphenylphosphino) propane, 1,2-bis(di-phenyl phosphino)butane, 1,1′-bis(di-phenylphosphino)ferrocene, N-(2-methoxyphenyl)-2-(di-t-butylphosphino)pyrrole, 1-(2-methoxyphenyl)-2-(di-cyclohexylphosphino)pyrrole, N-phenyl-2-(di-t-butylphosphino)indol, N-phenyl-2-(di-t-butylphosphino)pyrrole, N-phenyl-2-(dicyclohexylphosphino)indol, N-phenyl-2-(di-cyclohexylphosphino)pyrrole and 1-(2,4,6-trimethylphenyl)-2(dicyclohexylphosphino)imidazole.

### Claim 23 (depends on 12)

The process according to claim 12, wherein the Pd(0)Ln complex is Pd[PPh3]4.

### Claim 24

A process for the preparation of a Pd(II) complex of formula 2a or 2b:
comprising reacting Pd(diolefin) (Hal)2 with (i) hydroxide in water, (ii) an alkoxide in at least one solvent, or (iii) hydroxide in an alcohol ROH, optionally in at least one solvent, in which each Hal is independently a halide, each R is independently H or an optionally substituted C1-15 straight-chain, branched or cyclic alkyl group and the diolefin is cyclooctadiene or norbornadiene.

### Claim 25

A process for the preparation of a L2Pd(H)(Hal) complex comprising the steps of:
a′. optionally preparing a Pd(II) complex of formula 2a or 2b:
comprising reacting Pd(diolefin)(Hal)2 with (i) hydroxide in water, (ii) an alkoxide in at least one solvent, or (iii) hydroxide in an alcohol ROH, optionally in at least one solvent, wherein each Hal is independently a halide, each R is independently H or an optionally substituted C1-15 straight-chain, branched or cyclic alkyl group and the diolefin is cyclooctadiene or norbornadiene; and
b′. reacting the Pd(II) complex of formula 2a or 2b with ligand L and, if required, at least one solvent, to form the L2Pd(H)(Hal) complex;
wherein the at least one solvents of steps a′ and b′ are independently the same or different.

### Claim 26 (depends on 25)

The process according to claim 25, further comprising the step of:
c′. forming a Pd(0)Ln complex wherein n is 2, 3 or 4.

### Claim 27

A Pd(II) complex of formula 2a:
wherein each Hal is independently a halide, and each R is independently a substituted C1-15 straight-chain alkyl group, or an optionally substituted C1-15 branched or cyclic alkyl group.

### Claim 28

A Pd(II) complex of formula 2b:
wherein each Hal is independently a halide, and each R is independently H or an optionally substituted C1-15 straight-chain, branched or cyclic alkyl group.

### Claim 29

A Pd(0)L2 complex which is [t-Bu2(p-PhMe2N)P]2Pd.