Chemistry Letters, Vol.36, No.5, 650-651, 2007
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
Treatment of a tungsten bis(silyl) complex CP*W{kappa(3)-(Si,Si,O)-xantsil}(CO)(H) [xantsil = (9,9-dimethylxanthene4,5-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[kappa(3)(Si,Si,C)-(SiMe2){SiMe(NC5H3NMe2)}-(C15H12O)](CO)(H) can be regarded as the resonance hybrid of silyl-carbene and pyridyl-silylene complexes.