Catalytic hydrogenation using complexes of base metals with tridentate ligands

Patent metadata

Field	Value
Publication number	US-9566577-B1
Application number	US-201615256492-A
Country	US
Kind code	B1
Filing date	Sep 2, 2016
Priority date	Aug 16, 2012
Publication date	Feb 14, 2017
Grant date	Feb 14, 2017

Abstract

Complexes of cobalt and nickel with tridentate ligand PNHP R are effective for hydrogenation of unsaturated compounds. Cobalt complex [(PNHP Cy )Co(CH 2 SiMe 3 )]BAr F 4 (PNHP Cy =bis[2-(dicyclohexylphosphino)ethyl]amine, BAr F 4 =B(3,5-(CF 3 ) 2 C 6 H 3 ) 4 )) was prepared and used with hydrogen for hydrogenation of alkenes, aldehydes, ketones, and imines under mild conditions (25-60° C., 1-4 atm H 2 ). Nickel complex [(PNHP Cy )Ni(H)]BPh 4 was used for hydrogenation of styrene and 1-octene under mild conditions. (PNP Cy )Ni(H) was used for hydrogenating alkenes.

First claim

What is claimed is:

1. A process for hydrogenation of an unsaturated compound, the process comprising:
combining a composition comprising a compound of Formula 1 with hydrogen and an unsaturated compound under conditions effective for the hydrogenation of the unsaturated compound:

wherein:
each R 1 is independently selected from cycloalkyl, alkyl, substituted alkyl, phenyl, or substituted phenyl;
R 2 is —CH 2 Si(CH 3 ) 3 , H, alkyl, substituted alkyl, phenyl, substituted phenyl, alkoxide, or amido; and
M is cobalt or nickel.

2. The process of claim 1 , wherein R 2 is —CH 2 Si(CH 3 ) 3 , H, or alkyl.

3. The process of claim 1 , wherein R 2 is —CH 2 Si(CH 3 ) 3 , H, CH 3 , or CH 2 (CH 2 ) 6 CH 3 .

4. The process of claim 1 , wherein the unsaturated compound comprises:
a carbon-carbon double or triple bond that becomes hydrogenated as a result of the process,
a carbon-oxygen double bond that becomes hydrogenated as a result of the process, or
a carbon-nitrogen double or triple bond that becomes hydrogenated as a result of the process.

5. The process of claim 1 , wherein the combining the composition with hydrogen further comprises adding Hg or water.

6. The process of claim 1 , wherein the combining the composition of Formula 1 with hydrogen comprises combining a solution of the composition with the hydrogen and the unsaturated compound.

7. A process for hydrogenation of an unsaturated compound, the process comprising:
combining a composition comprising a compound of Formula 1 or Formula 2 with hydrogen and an unsaturated compound under conditions effective for the hydrogenation of the unsaturated compound:

wherein:
each R 1 is independently selected from cyclohexyl, isopropyl, adamantyl, or phenyl;
R 2 is —CH 2 Si(CH 3 ) 3 , H, alkyl, substituted alkyl, phenyl, substituted phenyl, alkoxide, or amido;
M is cobalt or nickel; and
X is a counterion.

8. The process of claim 7 , wherein R 2 is —CH 2 Si(CH 3 ) 3 , H, or alkyl.

9. The process of claim 7 , wherein R 2 is —CH 2 Si(CH 3 ) 3 , H, CH 3 , or CH 2 (CH 2 ) 6 CH 3 .

10. The process of claim 7 , wherein the unsaturated compound comprises:
a carbon-carbon double or triple bond that becomes hydrogenated as a result of the process,
a carbon-oxygen double bond that becomes hydrogenated as a result of the process, or
a carbon-nitrogen double or triple bond that becomes hydrogenated as a result of the process.

11. The process of claim 7 , wherein the combining the composition of Formula 1 or Formula 2 with hydrogen further comprises adding Hg or water.

12. The process of claim 7 , wherein the combining the composition of Formula 1 or Formula 2 with hydrogen comprises combining a solution of the composition of Formula 1 or Formula 2 with the hydrogen and the unsaturated compound.

13. The process of claim 7 , wherein the compound comprises: (PNP Cy )Co(CH 2 SiMe 3 ),
[(PNHP Cy )Co(CH 2 SiMe 3 )][X],
(PNP Cy )Co(H),
[(PNHP Cy )Co(H)][X],
(PNP Ad )Co(CH 2 SiMe 3 ),
[(PNHP Ad )Co(CH 2 SiMe 3 )][X],
(PNP iPr )Co(CH 2 SiMe 3 ),
[(PNHP iPr )Co(CH 2 SiMe 3 )][X],
(PNP Cy )Ni(H),
[(PNHP Cy )Ni(H)][X],
(PNP Cy )Ni(CH 2 (CH 2 ) 6 CH 3 ),
[(PNHP Cy )Ni(CH 2 (CH 2 ) 6 CH 3 )][X],
(PNP Cy )Ni(CH 3 ), or
[(PNHP Cy )Ni(CH 3 )][X],
wherein:
Cy is cyclohexyl,
Ad is adamantyl,
iPr is isopropyl, and
X is tetraphenylborate, hexafluorophosphate, B(C 6 F 5 ) 4 , or B(3,5-(CF 3 ) 2 C 6 H 3 ) 4 .

14. The process of claim 13 , wherein X is tetraphenylborate or hexafluorophosphate.

15. A composition comprising a compound represented by Formula 1 or Formula 2:

wherein:
each R 1 is independently selected from cyclohexyl, isopropyl, adamantyl, or phenyl;
R 2 is —CH 2 Si(CH 3 ) 3 , H, alkyl, substituted alkyl, phenyl, substituted phenyl, alkoxide, or amido;
M is cobalt or nickel; and
X is a counterion.

16. The composition of claim 15 , wherein R 2 is —CH 2 Si(CH 3 ) 3 , H, or alkyl.

17. The composition of claim 15 , wherein R 2 is —CH 2 Si(CH 3 ) 3 , H, CH 3 , or CH 2 (CH 2 ) 6 CH 3 .

18. The composition of claim 15 , wherein the compound is represented by Formula 2 in which the counterion X is tetraphenylborate, hexafluorophosphate, B(C 6 F 5 ) 4 , or B(3,5-(CF 3 ) 2 C 6 H 3 ) 4 .

19. The composition of claim 15 , wherein the compound comprises:
(PNP Cy )Co(CH 2 SiMe 3 ),
[(PNHP Cy )Co(CH 2 SiMe 3 )][X],
(PNP Cy )Co(H),
[(PNHP Cy Y)Co(H)][X],
(PNP Ad )Co(CH 2 SiMe 3 ),
[(PNHP Ad )Co(CH 2 SiMe 3 )][X],
(PNP iPr )Co(CH 2 SiMe 3 ),
[(PNHP iPr )Co(CH 2 SiMe 3 )][X],
(PNP Cy )Ni(H),
[(PNHP Cy )Ni(H)][X],
(PNP Cy )Ni(CH 2 (CH 2 ) 6 CH 3 ),
[(PNHP Cy )Ni(CH 2 (CH 2 ) 6 CH 3 )][X],
(PNP Cy )Ni(CH 3 ), or
[(PNHP Cy )Ni(CH 3 )][X],
wherein:
Cy is cyclohexyl,
Ad is adamantyl,
iPr is isopropyl, and
X is tetraphenylborate, hexafluorophosphate, B(C 6 F 5 ) 4 , or B(3,5-(CF 3 ) 2 C 6 H 3 ) 4 .

20. The composition of claim 19 , wherein X is tetraphenylborate or hexafluorophosphate.

Assignees

• Los Alamos Nat Security Llc

Inventors

• Hanson Susan K
• Zhang Guoqi
• Vasudevan Kalyan V

Classifications

• C07C45/62

  by hydrogenation of carbon-to-carbon double or triple bonds · CPC title

• C07C67/303

  by hydrogenation of unsaturated carbon-to-carbon bonds · CPC title

• C07C29/141

  with hydrogen or hydrogen-containing gases · CPC title

• C07C5/05

  Partial hydrogenation · CPC title

• C07C2102/08

  Chemistry & Metallurgy · mapped topic