Unfolding the crucial role of a nucleophile in Ziegler–Natta type Ir catalyzed polyaminoborane formation

Abstract

PAB formation through dehydropolymerization of ammonia-borane by Brookhart's iridium pincer catalyst has been under intense scrutiny but a sound molecular level understanding has remained elusive. Herein, using DFT the mechanism outlined by us for IrH₂POCOP catalyzed PAB formation underscores the importance of generation of nucleophiles, in particular that of the metal bound NH₂BH₂ moiety armed with a nitrogen lone pair for chain initiation and chain propagation steps.