First row metal-based catalysts for hydosilylation

Patent metadata

Field	Value
Publication number	US-9458185-B2
Application number	US-201314377833-A
Country	US
Kind code	B2
Filing date	Feb 11, 2013
Priority date	Feb 10, 2012
Publication date	Oct 4, 2016
Grant date	Oct 4, 2016

Abstract

In various embodiments, the invention provides phosphine ligand supported first row metal catalysts with surprising and efficacious catalytic activity for hydrosilylation of pi-bonded substrates. Also provided are methods of using the catalysts of the invention to prepare hydrosilylated compounds.

First claim

What is claimed is:

1. A cationic compound which comprises a first row metal atom supported on a phosphorus-containing ligand, wherein said ligand has the formula:

wherein
R o is a member selected from substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl and amine;
R a , R b , R c , R d , R e , R f , R a′ , R b′ , R c′ , R d′ , R e′ , and R f′ are members independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, halogen, CN, CF 3 , acyl, —SO 2 NR 8 R 9 , —NR 8 R 9 , —OR 8 , —S(O) 2 R 8 , —C(O)R 9 , —COOR 8 , —CONR 8 R 9 , —S(O) 2 OR 8 , —OC(O)R 8 , —C(O)NR 8 R 9 , —NR 8 C(O)R 9 , —NR 8 SO 2 R 9 and —NO 2 , wherein two or more of R a , R b , R c , R d , R e , R f , R a′ , R b′ , R c′ , R d′ , R e′ , and R f′ , together with the atoms to which they are bonded, are optionally joined to form a ring system which is a member selected from substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl
wherein
R 8 and R 9 are members independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl and substituted or unsubstituted heterocycloalkyl, and R 8 and R 9 , together with the atoms to which they are bonded, are optionally joined to form a 5- to 7-membered ring.

2. The compound according to claim 1 , wherein R o has the formula:

wherein
R g and R g′ are members selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, halogen, CN, CF 3 , acyl, —SO 2 NR 10 R 11 , —NR 10 R 11 , —OR 10 , —S(O) 2 R 10 , —C(O)R 11 , —COOR 10 , —CONR 10 R 11 , —S(O) 2 OR 10 , —OC(O)R 10 , —C(O)NR 10 OR 11 , —NR 10 C(O)R 11 , —NR 10 SO 2 R 11 and —NO 2 , wherein two or more of R a , R b , R c , R d , R e , R f , R a′ , R b′ , R c′ , R d′ , R e′ , and R f′ , together with the atoms to which they are bonded, are optionally joined to form a ring system which is a member selected from substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl
wherein
R 10 and R 11 are members independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl and substituted or unsubstituted heterocycloalkyl, and R 10 and R 11 , together with the atoms to which they are bonded, are optionally joined to form a 5- to 7-membered ring.

3. The compound according to claim 1 , wherein said ligand has a formula which is a member selected from:

4. The compound according to claim 1 , having the formula:
[II-M(X) s-t ] t+ [Y − ] t t−
in which
II is said ligand, which has a structure according to Formula II;
M is said first row metal atom;
X is a ligand for said metal atom;
Y − is an anion; and
s and t are integers independently selected from 0, 1, 2, 3 and 4 and are selected such that s-t is 0, 1, 2 or 3.

5. The compound according to claim 1 , wherein said compound catalyzes the addition of a hydrosilane across a pi-bonded system.

6. The compound according to claim 1 , wherein said compound catalyzes the addition of a hydrosilane across a pi-bonded system which is a member selected from a double bond of an alkene and a triple bond of an alkyne.

7. The compound according to claim 1 , wherein said first row metal atom is a member selected from a nickel atom, a copper atom, an iron atom and a cobalt atom.

8. A method of hydrosilylating a pi-bonded system, said method comprising: contacting said pi-bonded system with a compound according to claim 1 , which is a catalyst for said hydrosilylating said system and a hydrosilane under conditions appropriate for said hydrosilylating.

9. A method of hydrosilylating a pi-bonded system, wherein said pi-bonded system is a member selected from an alkene, an alkyne, and a carbonyl, said method comprising: contacting said pi-bonded system with a compound according to claim 1 , which is a catalyst for said hydrosilylating and a hydrosilane under conditions appropriate for said hydrosilylating.

10. The method according to claim 8 , wherein said hydrosilane is a member selected from a primary, secondary and tertiary hydrosilane.

Assignees

• Univ California

Inventors

• Tilley T Don
• Yang Jian

Classifications

• B01J2531/847

  Nickel · CPC title

• B01J31/1895

  the ligands containing arsenic or antimony · CPC title

• B01J2231/323

  Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation · CPC title

• C07F7/0896

  Compounds with a Si-H linkage · CPC title

• B01J31/22

  Organic complexes · CPC title