The First Resonance Hybrid of Silyl–Carbene and Pyridyl–Silylene Complexes: Formation by Aryl C–H Bond Activation of DMAP [4-(Dimethylamino)pyridine] on a Silylene Complex

Abstract

Abstract Treatment of a tungsten bis(silyl) complex Cp*W{κ3(Si,Si,O)-xantsil}(CO)(H) [xantsil = (9,9-dimethylxanthene-4,5-diyl)bis(dimethylsilyl)] with 4-(dimethylamino)pyridine (DMAP) causes ortho-metallation in a DMAP-stabilized silylene complex that is generated from the bis(silyl) complex through silicon-to-tungsten 1,2-methyl migration and methane elimination. Resulting W–Si–N–C four-membered metallacycle Cp*W[κ3(Si,Si,C)-(SiMe2){SiMe(NC5H3NMe2)}(C15H12O)](CO)(H) can be regarded as the resonance hybrid of silyl–carbene and pyridyl–silylene complexes.