Catalyst and battery components derived from condensation reactions with carba-closo-dodecaborate amines

Patent metadata

Field	Value
Publication number	US-9994595-B2
Application number	US-201515126245-A
Country	US
Kind code	B2
Filing date	Mar 16, 2015
Priority date	Mar 14, 2014
Publication date	Jun 12, 2018
Grant date	Jun 12, 2018

Abstract

Described herein is the fusion of two families of unique carbon-containing molecules that readily disregard the tendency of carbon to form four chemical bonds, namely N-heterocyclic carbenes (NHCs) and carborane anions. Deprotonation of an anionic imidazolium salt with lithium diisopropylamide at room temperature leads to a mixture of lithium complexes of C-2 and C-5 dianionic NHC constitutional isomers as well as a trianionic (C-2, C-5) adduct. Judicious choice of the base and reaction conditions allows for the selective formation of all three stable polyanionic carbenes. In solution, the so-called abnormal C-5 NHC lithium complex slowly isomerizes to the normal C-2 NHC, and the process can be proton catalyzed by the addition of the anionic imidazolium salt. These results indicate that the combination of two unusual forms of carbon atoms can lead to unexpected chemical behavior, and that this strategy paves the way for the development of a broad new generation of NHC ligands for catalysis.

First claim

What is claimed is:

1. A carborane compound according to Formula 1:

wherein:
Het N is an N-heterocyclic carbene (NHC) moiety;
R B is a carba-closo-dodecaborate substituent;
R W is selected from the group consisting of R B , H, halogen, alkyl, aryl, silyl, siloxy, alkoxy, and aryloxy,
wherein R B , alkyl, aryl, silyl, siloxy, alkoxy, and aryloxy in R W are optionally substituted with at least one member independently selected from the group consisting of halogen, hydroxyl, hydroxide, alkyl, aryl, silyl, siloxy, alkoxy, aryloxy, amino, alkylamino, arylamino, dialkylamino, diarylamino, haloalkyl, thio, alkylcarbonyl, cyano, carbamoyl, alkoxycarbamoyl, methylendioxy, carboxy, alkoxycarbonyl, aminocarbonyl, alkyaminocarbonyl, dialkylaminocarbonyl, and nitro; and
A is absent, or
A represents one or more cations, each of which is optionally coordinated by 1-8 neutral or anionic ligands.

2. The carborane compound according to claim 1 , wherein alkyl, aryl, silyl, siloxy, alkoxy, and aryloxy in R W are optionally substituted with a member independently selected from the group consisting of hydrogen, halogen, hydroxyl, and hydroxide.

3. The carborane compound according to claim 1 , wherein R W is selected from alkyl and aryl.

4. The carborane compound according to claim 1 , the compound having a structure according to Formula 2:

5. The carborane compound according to claim 1 , wherein Het N is selected from the group consisting of:

6. The carborane compound according to claim 1 , wherein R B has the structure

wherein each unlabeled vertex is a boron atom substituted with one R 1 group; and
each R 1 is independently selected from H, halogen, hydroxyl, hydroxide, alkyl, aryl, silyl, siloxy, alkoxy, aryloxy, amino, alkylamino, arylamino, dialkylamino, diarylamino, haloalkyl, thio, alkylcarbonyl, cyano, carbamoyl, alkoxycarbamoyl, methylendioxy, carboxy, alkoxycarbonyl, aminocarbonyl, alkyaminocarbonyl, dialkylaminocarbonyl, nitro, and alkoxy,
wherein each alkyl, aryl, silyl, siloxy, alkoxy, and aryloxy in R 1 is optionally substituted with a member independently selected from the group consisting of halogen, hydroxyl, hydroxide, alkyl, aryl, silyl, siloxy, alkoxy, aryloxy, amino, alkylamino, arylamino, dialkylamino, diarylamino, haloalkyl, thio, alkylcarbonyl, cyano, carbamoyl, alkoxycarbamoyl, methylendioxy, carboxy, alkoxycarbonyl, aminocarbonyl, alkyaminocarbonyl, dialkylaminocarbonyl, and nitro.

7. The carborane compound according to claim 6 , wherein
each R 1 is independently selected from H, halogen, alkyl, aryl, silyl, siloxy, alkoxy, and aryloxy, and wherein
each alkyl, aryl, silyl, siloxy, alkoxy, and aryloxy in R 1 is optionally substituted with a member independently selected from the group consisting of halogen, hydroxyl, and hydroxide.

8. The carborane compound according to claim 6 , wherein each R 1 is independently selected from the group consisting of H, alkyl, F, Cl, Br, and I.

9. The carborane compound according to claim 8 , wherein five R 1 are H in each R B group and each of the remaining six R 1 groups is independently selected from the group consisting of alkyl, F, Cl, Br, and I in each R B group.

10. The carborane compound according to claim 8 , wherein each of the eleven R 1 groups in each R B group is independently selected from the group consisting of alkyl, F, Cl, Br, and I.

11. The carborane compound according to claim 6 , wherein Het N is selected from the group consisting of:

12. The carborane compound according to claim 1 , wherein A is selected from the group consisting of Li + , HN(alkyl) 3 + , N(alkyl) 4 + , and Mg 2+ .

13. A carborane compound having a structure selected from the group consisting of Formula (I), Formula (II), Formula (III), Formula (IV), Formula (V), Formula (VI), Formula (VII), Formula (VIII), Formula (IX), Formula (X), Formula (XI), Formula (XII), Formula (XIII), Formula (XIV), Formula (XV), Formula (XVI), and Formula (XVII):

wherein each unlabeled vertex bonded to R 1 represents a boron atom,
wherein each R 1 and each R 2 is independently selected from the group consisting of H, halogen, alkyl, aryl, silyl, siloxy, alkoxy, and aryloxy;
wherein each alkyl, aryl, silyl, siloxy, alkoxy, and aryloxy is optionally substituted with a member independently selected from the group consisting of halogen, hydroxyl, and hydroxide; and
wherein A is a cation.

14. The carborane compound according to claim 13 , having the following structure:

15. The carborane compound according to claim 13 , having the following structure:

16. The carborane compound according to claim 13 , having the following structure:

17. The carborane compound according to claim 13 , having the following structure:

wherein each R 3 is independently selected from the group consisting of H, hydroxyl, hydroxide, and halogen.

18. The carborane compound according to any of claims 14 - 17 , wherein each R 1 is independently selected from the group consisting of H, alkyl, F, Cl, Br, and I.

19. A carbene complex comprising a transition metal and a carborane compound according to claim 13 .

20. A complex according to claim 19 , wherein the transition metal is selected from the group consisting of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, and Au.

21. A method of forming a carbon-carbon bond, the method comprising forming a reaction mixture comprising a carbene complex according to claim 19 , a carbene transfer agent, and a substrate having at least one carbon-hydrogen bond under conditions sufficient for the insertion of the carbene into the carbon-hydrogen bond.

22. A process for preparing a compound according to Formula (C):

the process comprising condensing a compound according to Formula (A)

with a compound according to Formula (B)

Assignees

• The Regents Of The Unversity Of California
• Univ California

Inventors

• Lavallo Vincent
• El Hellani Ahmad
• Chan Allen

Classifications

• B01J2531/824

  Palladium · CPC title

• B01J2531/827

  Iridium · CPC title

• C07F15/006

  Palladium compounds · CPC title

• C07F15/04

  Nickel compounds · CPC title

• C07C5/3337

  of the platinum group · CPC title