Backfunctionalized imidazolinium salts and NHC carbene-metal complexes

Patent metadata

Field	Value
Publication number	US-10975038-B2
Application number	US-201916548472-A
Country	US
Kind code	B2
Filing date	Aug 22, 2019
Priority date	Oct 9, 2014
Publication date	Apr 13, 2021
Grant date	Apr 13, 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 backfunctionalized imidazolinium salt selected from the group of formulae consisting of:

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;
each of R 5 and R 6 being separately selected from the group consisting of a partially fluorinated alkyl group, a fluorinated aryl group, an aliphatic group, and an aryl group; and
X is an anion.

2. The backfunctionalized imidazolinium salt of claim 1 , wherein X is a halogen anion.

3. The backfunctionalized imidazolinium salt of claim 1 , wherein R 1 is in a trans-configuration with respect to R 2 .

4. A free N-heterocyclic carbene synthesized by deprotonation of the backfunctionalized imidazolinium salt of claim 1 , wherein deprotonation includes reacting the backfunctionalized imidazolinium salt with silver oxide.

5. An N-heterocyclic carbene-metal complex comprising:
a metal; and
a first ligand comprising the free N-heterocyclic carbene of claim 4 , the first ligand being coordinated to the metal.

6. The N-heterocyclic carbene-metal complex of claim 5 , wherein the metal is selected from the group consisting of rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, and gold.

7. The N-heterocyclic carbene-metal complex of claim 5 , further comprising:
a second ligand comprising another free N-heterocyclic carbene of claim 4 , the second ligand being coordinated to the metal.

8. The N-heterocyclic carbene-metal complex of claim 7 , further comprising:
a third ligand selected from the group consisting of an acetylacetonate, alkoxy, alkyl, aryl, aryloxy, carbonyl, halide, imido, oxo, pyridine, trialkylphosphine, and triarylphosphine, the third ligand being coordinated to the metal.

9. The N-heterocyclic carbene-metal complex of claim 5 , further comprising:
a second ligand selected from the group consisting of an acetylacetonate, alkoxy, alkyl, aryl, aryloxy, carbonyl, halide, imido, oxo, pyridine, trialkylphosphine, and triarylphosphine, the second ligand being coordinated to the metal.

10. A method of synthesizing the backfunctionalized imidazolinium salt of claim 1 , the method comprising:
formamidine cyclization of a halogenated acrylate ester with Hünig's base in a solvent.

11. The method of claim 10 , wherein the solvent is selected from the group consisting of toluene and acetone.

12. The method of claim 10 , further comprising:
introducing a base during the formamidine cyclization.

13. The method of claim 12 , wherein the base is selected from the group consisting of triethylamine, formamidine, and Hünig's base.

14. The method of claim 10 , further comprising:
preparing halogenated, acrylate ester from an acrylate ester.

Assignees

• Us Gov Air Force
• Us Air Force

Inventors

• Blanski Rusty L
• Grubbs Robert H

Classifications

• C07F15/0033

  Iridium compounds · CPC title

• C07F15/0046

  Ruthenium compounds · CPC title

• 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