公开(公告)号：US09994595B2

公开(公告)日：2018-06-12

申请号：US15126245

申请日：2015-03-16

申请人： THE REGENTS OF THE UNVERSITY OF CALIFORNIA

发明人： Vincent Lavallo ,  Ahmad El Hellani ,  Allen Chan

IPC分类号： C07F5/02 ,  C07F15/00 ,  C07F15/04 ,  C07F1/00 ,  C07F1/08 ,  C07F1/10 ,  C07F3/02 ,  B01J31/22 ,  B01J31/24 ,  C07C2/76 ,  C07C5/333 ,  H01M10/0565 ,  H01M10/0568

CPC分类号： C07F5/027 ,  B01J31/2265 ,  B01J31/2295 ,  B01J31/2404 ,  B01J2231/46 ,  B01J2231/766 ,  B01J2531/16 ,  B01J2531/17 ,  B01J2531/824 ,  B01J2531/827 ,  B01J2531/847 ,  C07C2/76 ,  C07C5/3335 ,  C07C5/3337 ,  C07C2531/22 ,  C07F1/00 ,  C07F1/08 ,  C07F1/10 ,  C07F3/02 ,  C07F5/02 ,  C07F15/0033 ,  C07F15/006 ,  C07F15/04 ,  C07F15/045 ,  H01M10/0565 ,  H01M10/0568 ,  H01M2300/0025 ,  H01M2300/0085

摘要： 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.