First row metal-based catalysts for hydosilylation

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.