Backfunctionalized imidazolinium salts and NHC carbene-metal complexes

Patent metadata

Field	Value
Publication number	US-10913723-B2
Application number	US-201916548501-A
Country	US
Kind code	B2
Filing date	Aug 22, 2019
Priority date	Oct 9, 2014
Publication date	Feb 9, 2021
Grant date	Feb 9, 2021

Abstract

Backfunctionalized imidazolinium salts and methods of synthesizing the same and NHC carbene-metal complexes therefrom. For backfunctionalized imidazolinium salts of the formula:

Wherein R 1 is selected from the group consisting of an ester group, an amide group, and an aromatic group; R 2 is selected from the group consisting of hydrogen, an ester group, an amide group, and an aromatic group; R 3 and R 4 are each an aliphatic group; and X is an anion; the method comprises cyclization of a halogenated acrylate with Hünig's base in a solvent.

First claim

What is claimed is:

1. A method of synthesizing an N-heterocyclic carbene-metal complex, the method comprising:
synthesizing a backfunctionalized imidazolinium salt by formamidine cyclization of a halogenated acrylate with a primary base in a solvent, the primary base being Hünig's base, the backfunctionalized imidazolinium salt comprising the formula:

R 1 being selected from the group consisting of an ester group, an amide group, and an aromatic group;
R 2 being selected from the group consisting of hydrogen, an ester group, an amide group, and an aromatic group;
each of R 3 and R 4 being separately selected from the group consisting of a C 1 -C 20 alkyl group, C 1 -C 20 partially fluorinated alkyl group, an aryl group, an aryl group with para CF 3 functionality, an aryl group having C 1 -C 20 partially fluorinated alkyl groups or partially fluorinated alkoxy groups, and a C 1 -C 20 partially fluorinated aliphatic group, and a C 1 -C 20 aryl group; and
X is an anion;
forming a free N-heterocyclic carbene by deprotonating the backfunctionalized imidazolinium salt via reacting the backfunctionalized imidazolinium salt with silver oxide; and
coordinating the free N-heterocyclic carbene to a metal as a first ligand.

2. The method of claim 1 , further comprising:
coordinating a second ligand to the metal, the second ligand being a second free N-heterocyclic carbene.

3. The method of claim 2 , further comprising:
coordinating a third ligand to the metal, the third ligand selected from the group consisting of an acetylacetonate, alkoxy, alkyl, aryl, aryloxy, carbonyl, halide, imido, oxo, pyridine, trialkylphosphine, and triarylphosphine.

4. The method of claim 1 , wherein the metal selected from the group consisting of rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, and gold.

5. The method of claim 1 , wherein the solvent in formamidine cyclization of the halogenated acrylate is a polar aprotic solvent.

6. The method of claim 5 , wherein the polar aprotic solvent is selected from the group consisting of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether.

7. The method of claim 1 , wherein the primary base in formamidine cyclization of the halogenated acrylate is Hünig's base.

Assignees

• Us Gov Air Force
• Us Air Force

Inventors

• Blanski Rusty L
• Grubbs Robert H

Classifications

• C07D233/28 Primary

  with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms · CPC title

• C07F15/0046

  Ruthenium compounds · CPC title

• C07F15/0033

  Iridium compounds · CPC title