In 2018, our group reported the synthesis of an 1,3-diketiminate manganese(II) dimer, [(2,6-iPr2PhBDI)Mn(μ-H)]2, which is active for the hydrosilylation of alkenes at elevated temperature. We also demonstrated silicone curing by way of Mn catalyzed olefin hydrosilylation for the first time. More recently, a thorough electronic structure evaluation of this dimer revealed that there is weak antiferromagnetic coupling between the Mn centers, which allows access to a catalytically relevant hydride monomer through dissociation. Upon discovering that this monomer is also active for the dihydroboration of nitriles to yield diborylamines, we sought to demonstrate the preparation of industrially-relevant aminosilane products through Mn-catalyzed dehydrogenative coupling. The synthesis of common chemical vapor deposition precursors through coupling of primary and secondary amines to the widely utilized industrial gas, SiH4, will be discussed. Extension of this work to the preparation of polycarbosilazanes and perhydropolysilazane has been demonstrated. Mechanistic studies indicate that amine activation leads to the formation of amido intermediates.

Preparing aminosilane chemical vapor deposition precursors and polycarbosilazanes through manganese catalysis

ACS Spring 2022

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.