First-row transition metal hydrogenation and hydrosilylation catalysts

Patent metadata

Field	Value
Publication number	US-10407451-B2
Application number	US-201715622276-A
Country	US
Kind code	B2
Filing date	Jun 14, 2017
Priority date	Jun 12, 2013
Publication date	Sep 10, 2019
Grant date	Sep 10, 2019

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

What is claimed is:

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.

Assignees

• Trovitch Ryan J
• Mukhopadhyay Tufan K
• Pal Raja
• Levin Hagit Ben Daat
• Porter Tyler M
• Ghosh Chandrani
• Univ Arizona State

Inventors

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

Classifications

• B01J2531/0255

  Ligands comprising the N2S2 or N2P2 donor atom set, e.g. diiminodithiolates or diiminodiphosphines with complete pi-conjugation between all donor centres · CPC title

• B01J31/189

  containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand · CPC title

• B01J31/00

  Catalysts comprising hydrides, coordination complexes or organic compounds (catalyst compositions used only in polymerisation reactions C08 {; catalytic antibodies C12N9/0002}) · CPC title

• C07F15/025

  without a metal-carbon linkage · CPC title

• B01J2531/842

  Iron · CPC title