Versatile Conversion of N-Heterocyclic Silylene to Silyl Metal Compounds by Insertion of Divalent Silicon into Metal-Carbon and Metal-Hydrogen Bonds

The facile one-pot reaction of the stable N-heterocyclic silylene LSi: 1 (L?(ArN)C(?CH2) CH?C(Me)(NAr), Ar=2,6-iPr2C6H3) with Me2Zn, Me3Al, H3Al-NMe3, and MeLi has been investigated. The silicon(II) atom in 1 is capable of insertion into the corresponding M?C and Al?H bonds under very mild reaction conditions. Thus, Me2Zn furnishes the bis(silyl) zinc complex LSi(Me)ZnSi(Me)L 2 as the sole product, irrespective of the molar ratio of the starting materials applied. Moreover, the reactions of 1 with Me3Al, H3Al-NMe3, and MeLi lead directly to the 1,1-addition products LSi(Me)(Al(thf)Me2) 3, LSi(H)(AlH2(NMe3)) 4, and LSi(Me)Li(thf)3 5, respectively. All new compounds 25 were fully characterized by multinuclear NMR spectroscopy, mass spectrometry, elemental analyses, and single-crystal X-ray diffraction analyses.