First-row transition metal hydrogenation and hydrosilylation catalysts

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

wherein:

M is Mn, Fe, Co, Ni, or a combination thereof;

each X is a donor group independently selected from PR 1 n and NR 1 n , where n=2, 1, or 0, wherein each R 1 is independently selected from an inert functional group, a substituted, unsubstituted, or cyclic C 1-24 alkyl group optionally having one or more heteroatoms, and an aryl or substituted aryl group that optionally contains one or more heteroatoms;

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 2-3 alkylene linking group but not an aryl functionality directly attached to N;

Z is absent, or is a hydride, an alkyl, an aryl, an alkoxide, an amide, a silyl, or a boryl;

and

wherein the metal complex is neutral.

2. The metal complex of claim 1 , wherein Z is hydride.

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

4. 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.

5. The method of claim 4 , wherein the reductant is a silane, a substituted silane, an alkoxysilane, hydrogen, a substituted borane, a substituted alane, or a mixture thereof.

6. The method of claim 4 , wherein the one or more organic substrates contain a ketone, an ester, or mixtures thereof.

7. The method of claim 6 , wherein the one or more organic substrates include an unsaturated organic compound.

8. The method of claim 7 , wherein the unsaturated organic compound is an olefin or an alkyne.

9. 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 .

10. The method of claim 9 , 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.

11. 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 .

12. The method of claim 11 , whereby the H atoms in the H 2 are added across an unsaturated bond in the unsaturated organic compound to reduce the unsaturated bond.

13. 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 a donor group independently selected from PR 1 n and NR 1 n , where n=2, 1, or 0, wherein each R 1 is independently selected from an inert functional group, a substituted, unsubstituted, or cyclic C 1-24 alkyl group optionally having one or more heteroatoms, and an aryl or substituted aryl group that optionally contains one or more heteroatoms;

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 aikoxide, an amide, a silyl, a boryl, and combinations thereof;

each Y is independently selected from a substituted or unsubstituted C 3 alkylene linking group but not an aryl functionality directly attached to N;

Z is absent, or is a hydride, an alkyl, an aryl, an alkoxide, an amide, a silyl, or a boryl;

or a salt thereof, and

wherein the metal complex is neutral or charged.

14. The metal complex of claim 13 , wherein:

Z is absent.

15. The metal complex of claim 13 , wherein:

Z is hydride.

16. A catalytic composition comprising the metal complex of claim 13 .

17. 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 13 in the presence of a reductant, whereby the one or more organic substrates are reduced.

18. 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 13 .

19. 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 13 .

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

wherein:

M is Ni;

each X is PR 1 n , where n=2, 1, or 0, wherein each R 1 is an aryl group;

each R is a C 1 alkyl group; and

each Y is a C 3 alkylene linking group.