First-row transition metal hydrogenation and hydrosilylation catalysts

Patent metadata

Field	Value
Publication number	US-2016176908-A1
Application number	US-201414896813-A
Country	US
Kind code	A1
Filing date	Jun 11, 2014
Priority date	Jun 12, 2013
Publication date	Jun 23, 2016
Grant date	—

Abstract

Transition metal compounds, and specifically transition metal compounds having a tetradentate and/or pentadentate supporting ligand are described, together with methods for the preparation thereof and the use of such compounds as hydrogenation and/or hydrosilylation catalysts.

First claim

1 . A first row transition metal complex having a tetradentate or pentadentate supporting ligand, wherein the metal complex comprises a chemical structure selected from the group consisting of:

wherein:
M is Mn, Fe, Co, Ni, or a combination thereof;
each X is independently selected from PR n , NR n , AsR n , SbR n , BiR n , OR n , SR n , SeR n , TeR n , and any other donor group, where n=2, 1, or 0, a heterocycle containing one of these donor atoms, and any combination thereof;
each R is independently selected from hydrogen, an inert functional group, a substituted, unsubstituted, or cyclic C 1-24 alkyl group optionally having one or more heteroatoms, an aryl or substituted aryl group that optionally contains one or more heteroatoms, a moiety where two R groups taken together form a ring that is a substituted or unsubstituted, saturated or unsaturated cylic structure that optionally contains one or more heteroatoms, a halogen, an alkoxide, an amide, a silyl, a boryl, and combinations thereof;
each Y is independently selected from a substituted or unsubstituted C 1-24 alkylene linking group optionally having one or more heteroatoms but not an aryl functionality directly attached to N;
Q is a substituted, unsubstituted, or cyclic C 1-24 alkylene linking group optionally having one or more heteroatoms, or an aryl or substituted aryl linking group that optionally contains one or more heteroatoms; and
Z is a hydride, an alkyl, an aryl, an alkoxide, an amide, a silyl, or a boryl;
or a salt thereof.

2 . The metal complex of claim 1 , wherein the chemical structure is selected from the group consisting of:

and salts thereof.

3 . The metal complex of claim 1 , wherein the chemical structure is selected from the group consisting of:

and salts thereof.

4 . The metal complex of claim 1 , wherein:
M is Mn, Fe, Co, or Ni; and each X is independently selected from PR 2 , NR 2 , and any other donor group.

5 . The metal complex of claim 3 , wherein Z is hydride.

6 . A catalytic composition comprising the metal complex of claim 1 .

7 . A method for reducing one or more organic substrates comprising contacting a composition comprising one or more organic substrates with a catalytic composition comprising a metal complex according to claim 1 in the presence of a reductant, whereby the one or more organic substrates are reduced.

8 . The method of claim 8 , wherein the reductant is a silane, a substituted silane, an alkoxysilane, hydrogen, a substituted borane, a substituted alane, or a mixture thereof.

9 . The method of claim 7 , wherein the one or more organic substrates contain a ketone, an ester, or mixtures thereof.

10 . The method of claim 9 , wherein the one or more organic substrates include an unsaturated organic compound.

11 . The method of claim 10 , wherein the unsaturated organic compound is an olefin or an alkyne.

12 . A method of facilitating a hydrosilylation reaction, comprising reacting a compound comprising an Si—H bond with an unsaturated organic compound in the presence of one or more of the metal complexes of claim 1 .

13 . The method of claim 12 , whereby the Si and H atoms in the Si—H bond are added across an unsaturated bond in the unsaturated organic compound to form an organosilicon compound.

14 . A method of facilitating a hydrogenation reaction, comprising reacting H 2 with an unsaturated organic compound in the presence of one or more of the metal complexes of claim 1 .

15 . The method of claim 14 , whereby the H atoms in the H 2 are added across an unsaturated bond in the unsaturated organic compound to reduce the unsaturated bond.

16 . (canceled)

Assignees

• Univ Arizona State

Inventors

• Trovitch Ryan J
• Mukhopadhyay Tufin K
• Pal Raja
• Levin Hagit Ben-Daat
• Porter Tyler M
• Ghosh Chandrani

Classifications

• C07F7/0805

  comprising only Si, C or H atoms · CPC title

• C07F15/045

  without a metal-carbon linkage · CPC title

• C07F9/5045

  Complexes or chelates of phosphines with metallic compounds or metals · CPC title

• B01J2531/847

  Nickel · CPC title

• B01J2531/845

  Cobalt · CPC title