Abstract and subjects
Compounds that feature Si–N bonds are of widespread importance to the electronics and coating industries. Aminosilanes and polysilazanes are currently prepared by adding amines to halosilanes, an inefficient methodology that generates stoichiometric quantities of ammonium salt waste. Herein, we describe the syntheses of aminosilane chemical vapor deposition precursors, polycarbosilazanes, and perhydropolysilazane through the ambient-temperature dehydrocoupling of amines to silane (SiH4). Specifically, the β-diketiminate manganese hydride dimer [(2,6‑iPr2PhBDI)Mn(μ-H)]2 has been used to catalyze the formation of commercial aminosilane monomers from secondary and primary amines, highly cross-linked polycarbosilazane powders from diamines and triamines, and perhydropolysilazane from ammonia. The mechanism of dehydrocoupling was explored, and the addition of isopropylamine to [(2,6‑iPr2PhBDI)Mn(μ-H)]2 resulted in σ-bond metathesis to eliminate H2 and generate [(2,6‑iPr2PhBDI)Mn(μ-NHiPr)]2. In the presence of SiH4, H–Si addition across newly formed Mn–N bonds regenerates the precatalyst, offering a straightforward catalytic cycle for halogen-free Si–N bond formation.