Reactions of PNP-supported silylene complexes [(PNP)(H)Ir═SiRR′][B(C6F5)4] (R = R′ = Ph (1) and R = H, R′ = Mes (2)) with Lewis bases, carbonyl compounds, alcohols, and amines were investigated. Addition of DMAP (4-dimethylaminopyridine) to 1 and 2 produced base-stabilized silylene complexes [(PNP)(H)IrSiRR′(DMAP)][B(C6F5)4] (R = R′ = Ph (3) and R = H, R′ = Mes (4)). Reactions of 2 with benzophenone and benzaldehyde afforded the products of stoichiometric hydrosilylation, heteroatom-substituted silylene complexes [(PNP)(H)Ir═SiMes(OCH(Ph)(R))][B(C6F5)4] (R = Ph (5) and R = H (6)). Complex 1 reacted with DMF or benzophenone, and 2 reacted with DMF, to afford base-stabilized silylene complexes of the type [(PNP)(H)IrSiRR′(B)][B(C6F5)4] (R = H, R′ = Mes, B = DMF (7); R = R′ = Ph, B = DMF (8) and O═CPh2 (9)). In contrast, treatment of 1 with acetophenone afforded {(PNPH)IrH[SiPh2(OC(═CH2)Ph)]}[B(C6F5)4] (10), from activation of a C−H bond at the α-carbon position of acetophenone. Reactions of alcohols and amines with 1 afforded [(PNPH)IrH(SiPh2OR)][B(C6F5)4] (R = 3,5-tBu2C6H3 (11), R = Ph (12), R = iPr (13), and R = tBu (14)) and [(PNPH)IrH(SiPh2NHR)][B(C6F5)4] (R = Ph (15), R = 3,5-(CF3)2C6H3 (16)). Exploration of the catalytic activity of iridium silylene complexes with these organic substrates demonstrated that 1 is an effective catalyst for silane alcoholysis and aminolysis and for the hydrosilylation of ketones.
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