Late first row transition metal aryl diimine catalysts for hydrofunctionalization and dehydrocoupling

Patent metadata

Field	Value
Publication number	US-12180232-B2
Application number	US-202217953546-A
Country	US
Kind code	B2
Filing date	Sep 27, 2022
Priority date	Sep 28, 2021
Publication date	Dec 31, 2024
Grant date	Dec 31, 2024

Abstract

Aryl diimine first row metal compounds are described, as well as their synthesis and use as catalysts for the hydrofunctionalization of unsaturated organic compounds and main group element-main group element bond formation by dehydrogenative coupling.

First claim

What is claimed is:

1. A method of facilitating a hydrofunctionalization reaction, the method comprising reacting a reductant having a H—H, H—B, H—Al, H—C, H—Si, H—N, H—P, H—O, H—S, or H—Se bond with an unsaturated organic compound having a double bond or triple bond in the presence of one or more aryl diimine complexes having a structure represented by one of general structures G-1.1 through G-1.15:

where:
each M represents Mn, Fe, Co, or Ni;
each Y independently represents PRn, NRn, AsRn, SbRn, BiRn, ORn, SRn, SeRn, TeRn, a heterocycle comprising P, N, As, Sb, Bi, O, S, Se, Te, and combinations thereof, wherein n=2, 1, or 0;
each X independently represents a substituted or unsubstituted C 1 -C 24 alkylene or arylene linking group optionally comprising one or more heteroatoms;
each R, including R under the definition of Y, independently represents hydrogen; a substituted, unsubstituted, or cyclic C 1 -C 24 alkyl group that optionally comprises one or more heteroatoms; an aryl or substituted aryl group that optionally comprises one or more heteroatoms; a ring formed from two R groups taken together that is a substituted or unsubstituted, saturated or unsaturated cyclic structure that optionally comprises one or more heteroatoms; a halide; an alkoxide; an amide; a silyl; a boryl; or any combination thereof; and
each Z independently represents a hydride, alkyl, aryl, halide, alkoxide, aryloxide, carboxylate, or amido substituent.

2. The method claim 1 , wherein the H—H, H—B, H—Al, H—C, H—Si, H—N, H—P, H—O, H—S, or H—Se bond of the reductant is added across the double bond or triple bond of the unsaturated organic compound to yield the saturated product (in the case of H—H) or monofunctionalized reduced product (in the case of H—B, H—Al, H—C, H—Si, H—N, H—P, H—O, H—S, or H—Se).

3. A method of facilitating a hydrofunctionalization reaction, the method comprising reacting a reductant having a H—H, H—B, H—Al, H—C, H—Si, H—N, H—P, H—O, H—S, or H—Se bond with an unsaturated organic compound having a double bond or triple bond in the presence of a base and one or more of the aryl diimine complexes of claim 2 .

4. The method of claim 3 , wherein the H—H, H—B, H—Al, H—C, H—Si, H—N, H—P, H—O, H—S, or H—Se bond of the reductant is added across the double bond or triple bond of the unsaturated organic compound to yield the saturated product (in the case of H—H) or monofunctionalized reduced product (in the case of H—B, H—Al, H—C, H—Si, H—N, H—P, H—O, H—S, or H—Se).

5. A method of facilitating a hydrofunctionalization reaction, the method comprising reacting a reductant having a H—H, H—B, H—Al, H—C, H—Si, H—N, H—P, H—O, H—S, or H—Se bond with an unsaturated organic compound having a double bond or triple bond in the presence of an organic solvent and one or more of the aryl diimine complexes of claim 1 .

6. The method of claim 5 , wherein the H—H, H—B, H—Al, H—C, H—Si, H—N, H—P, H—O, H—S, or H—Se bond of the reductant is added across the double bond or triple bond of the unsaturated organic compound to yield the saturated product (in the case of H—H) or monofunctionalized reduced product (in the case of H—B, H—Al, H—C, H—Si, H—N, H—P, H—O, H—S, or H—Se).

7. A method of facilitating a hydrofunctionalization reaction, the method comprising reacting a reductant having a H—H, H—B, H—Al, H—C, H—Si, H—N, H—P, H—O, H—S, or H—Se bond with an unsaturated organic compound having a double bond or triple bond in the presence of an organic solvent, a base, and one or more of the aryl diimine complexes of claim 1 .

8. The method of claim 7 , wherein the H—H, H—B, H—Al, H—C, H—Si, H—N, H—P, H—O, H—S, or H—Se bond of the reductant is added across the double bond or triple bond of the unsaturated organic compound to yield the saturated product (in the case of H—H) or monofunctionalized reduced product (in the case of H—B, H—Al, H—C, H—Si, H—N, H—P, H—O, H—S, or H—Se).

9. A method of facilitating a hydrofunctionalization reaction, the method comprising reacting a reductant having a H—H, H—B, H—Al, H—C, H—Si, H—N, H—P, H—O, H—S, or H—Se bond with an unsaturated organic compound having a double bond or triple bond in the presence of one or more salts comprising a cation or anion of one or more aryl diimine complexes having a structure represented by one of general structures G-1.1 through G-1.15:

where:
each M represents Mn, Fe, Co, or Ni;
each Y independently represents PR n , NR n , AsR n , SbR n , BiR n , OR n , SR n , SeR n , TeR n , a heterocycle comprising P, N, As, Sb, Bi, O, S, Se, Te, and combinations thereof, wherein n=2, 1, or 0;
each X independently represents a substituted or unsubstituted C 1 -C 24 alkylene or arylene linking group optionally comprising one or more heteroatoms;
each R, including R under the definition of Y, independently represents hydrogen; a substituted, unsubstituted, or cyclic C 1 -C 24 alkyl group that optionally comprises one or more heteroatoms; an aryl or substituted aryl group that optionally comprises one or more heteroatoms; a ring formed from two R groups taken together that is a substituted or unsubstituted, saturated or unsaturated cyclic structure that optionally comprises one or more heteroatoms; a halide; an alkoxide; an amide; a silyl; a boryl; or any combination thereof; and
each Z independently represents a hydride, alkyl, aryl, halide, alkoxide, aryloxide, carboxylate, or amido substituent.

10. The method of claim 9 , wherein the H—H, H—B, H—Al, H—C, H—Si, H—N, H—P, H—O, H—S, or H—Se bond of the reductant is added across the double bond or triple bond of the unsaturated organic compound to yield the saturated product (in the case of H—H) or monofunctionalized reduced product (in the case of H—B, H—Al, H—C, H—Si, H—N, H—P, H—O, H—S, or H—Se).

11. A method of facilitating a hydrofunctionalization reaction, the method comprising reacting a reductant having a H—H, H—B, H—Al, H—C, H—Si, H—N, H—P, H—O, H—S, or H—Se bond with an unsaturated organic compound having a double bond or triple bond in the presence of a base and one or more salts of claim 9 .

12. The method of claim 11 , wherein the H—H, H—B, H—Al, H—C, H—Si, H—N, H—P, H—O, H—S, or H—Se bond of the reductant is added across the double bond or triple bond of the unsaturated organic compound to yield the saturated product (in the case of H—H) or monofunctionalized reduced product (in the case of H—B, H—Al, H—C, H—Si, H—N, H—P, H—O, H—S, or H—Se).

13. A method of facilitating a hydrofunctionalization reaction, the method comprising reacting a reductant having a H—H, H—B, H—Al, H—C, H—Si, H—N, H—P, H—O, H—S, or H—Se bond with an unsaturated organic compound having a double bond or triple bond in the presence of an organic solvent and one or more salts of claim 9 .

14. The method of claim 13 , wherein the H—H, H—B, H—Al, H—C, H—Si, H—N, H—P, H—O, H—S, or H—Se bond of the reductant is added across the double bond or triple bond of the unsaturated organic compound to yield the saturated product (in the case of H—H) or mono functionalized reduced product (in the case of H—B, H—Al, H—C, H—Si, H—N, H—P, H—O, H—S, or H

Assignees

• Trovitch Ryan J
• Sharma Anuja
• Nguyen Thu Thao
• Univ Arizona State

Inventors

• Trovitch Ryan J
• Sharma Anuja
• Nguyen Thu Thao

Classifications

• C07F15/02

  Iron compounds · CPC title

• C07F15/06

  Cobalt compounds · CPC title

• C07F15/04

  Nickel compounds · CPC title

• C07F13/00 Primary

  Compounds containing elements of Groups 7 or 17 of the Periodic Table · CPC title

• C07F7/10 Primary

  containing nitrogen {having a Si-N linkage} · CPC title