ORGANONICKEL INTERMEDIATES USEFUL FOR CARBOXYLATION OF SUBSTRATES WITH CARBON DIOXIDE
The present disclosure relates to a compound having the structure where R 1 includes at least one of a methyl group, a halogen, a hydrogen, or a combination thereof, R 2 includes at least one of a benzyl group, an ether, or a combination thereof, R 3 includes at least one of hydrogen, a methyl group, or a combination thereof, and X includes a halogen.
1 . A compound comprising:
wherein:
R 1 comprises at least one of a methyl group, a halogen, a hydrogen, or a combination thereof,
R 2 comprises at least one of a benzyl group, an ether, or a combination thereof,
R 3 comprises at least one of hydrogen, a methyl group, or a combination thereof, and
X comprises a halogen.
2 . The compound of claim 1 , further comprising an alkyl linking group positioned between the nickel atom and R 2 .
3 . The compound of claim 2 , wherein the alkyl group is a —CH 2 -group.
4 . The compound of claim 1 , wherein Ri comprises at least one of —C(CH 3 ) 3 , —CF 3 , H, or a combination thereof.
5 . The compound of claim 1 , wherein X comprises at least one iodine, chlorine, bromine, or a combination thereof.
6 . The compound of claim 1 , wherein the benzyl group is selected from the group consisting of
and is a covalent bond between R 2 and Ni.
7 . The compound of claim 1 , wherein the ether is a linear molecule.
8 . The compound of claim 7 , wherein the linear molecule is selected from the group consisting of
and is a covalent bond between R 2 and Ni.
9 . The compound of claim 1 , wherein the ether is a cyclic molecule.
10 . The compound of claim 9 , wherein the cyclic molecule is selected from the group consisting of
and M is a covalent bond between R 2 and Ni.
12 . A method comprising:
reacting CO 2 and a nickel pre-catalyst with a reactant comprising at least one of a benzyl group, an ether, or a combination thereof to form a carboxylic acid, wherein:
the nickel pre-catalyst comprises:
R 1 comprises at least one of a methyl group, a halogen, or a combination thereof,
R 3 comprises at least one of hydrogen, a methyl group, or a combination thereof, and
X comprises a halogen.
13 . The method of claim 12 , wherein the reacting further comprises irradiating the nickel pre-catalyst with light having a wavelength between 300 nm and 800 nm or between 350 nm and 500 nm.
14 . The method of claim 12 , wherein the reacting further comprises a photosensitizer.
15 . The method of claim 12 , wherein the reacting further comprises a base.
16 . The method of claim 12 , wherein the reacting further comprises a sacrificial reductant.
17 . The method of claim 12 , wherein:
the reacting further comprises forming an intermediate compound that reacts to form the carboxylic acid, and
the intermediate compound comprises:
and
R 2 comprises at least one of the benzyl group, the ether, or a combination thereof.
18 . The method of claim 12 , wherein the carboxylic acid comprises at least one of
or a combination thereof.
19 . The method of claim 12 , wherein the reactant comprises at least one of
or a combination thereof.
20 . The method of claim 17 , further comprising, prior to reacting CO 2 and the nickel pre-catalyst with the reactant:
reacting a ligand with a nickel complex to form the nickel pre-catalyst, wherein:
the ligand comprises
and the nickel complex comprises