# US 12,180,232 B2 · Late first row transition metal aryl diimine catalysts for hydrofunctionalization and dehydrocoupling

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- Number: US 12,180,232 B2
- Document ID: US12180232B2
- Status: Granted
- Kind: B2
- Application number: 17/953,546
- Filed: 2022-09-27
- Published: 2023-04-13
- Granted: 2024-12-31
- Earliest claimed: 2021-09-28
- Assignees: Arizona Board of Regents on behalf of Arizona State University
- Applicants: Ryan J. Trovitch; Anuja Sharma; Thu Thao Nguyen
- Inventors: Ryan J. Trovitch; Anuja Sharma; Thu Thao Nguyen
- Web page: https://patentgrep.com/patent/US12180232B2

## CPC

- C07F 7/10: containing nitrogen {having a Si-N linkage}
- C07F 13/00: Compounds containing elements of Groups 7 or 17 of the Periodic Table
- C07F 15/02: Iron compounds
- C07F 15/04: Nickel compounds
- C07F 15/06: Cobalt compounds
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)

## 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.

## Claims

### Claim 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 C1-C24 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 C1-C24 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.

### Claim 2 (depends on 1)

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).

### Claim 3 (depends on 2)

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.

### Claim 4 (depends on 3)

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).

### Claim 5 (depends on 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 an organic solvent and one or more of the aryl diimine complexes of claim 1.

### Claim 6 (depends on 5)

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).

### Claim 7 (depends on 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 an organic solvent, a base, and one or more of the aryl diimine complexes of claim 1.

### Claim 8 (depends on 7)

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).

### Claim 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 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 C1-C24 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 C1-C24 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.

### Claim 10 (depends on 9)

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).

### Claim 11 (depends on 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 a base and one or more salts of claim 9.

### Claim 12 (depends on 11)

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).

### Claim 13 (depends on 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 an organic solvent and one or more salts of claim 9.

### Claim 14 (depends on 13)

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—Se).

### Claim 15 (depends on 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 an organic solvent, a base, and one or more salts of claim 9.

### Claim 16 (depends on 15)

The method of claim 15, 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).