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(=CH(2))CH=C(Me)(NAr), Ar=2,6-iPr(2)C(6)H(3)) with Me(2)Zn, Me(3)Al, H(3)Al-NMe(3), 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, Me(2)Zn 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 Me(3)Al, H(3)Al-NMe(3), and MeLi lead directly to the 1,1-addition products LSi(Me)(Al(thf)Me(2)) 3, LSi(H)(AlH(2)(NMe(3))) 4, and LSi(Me)Li(thf)(3) 5, respectively. All new compounds 2-5 were fully characterized by multinuclear NMR spectroscopy, mass spectrometry, elemental analyses, and single-crystal X-ray diffraction analyses.