Versatile conversion of N-heterocyclic silylene to silyl metal compounds by insertion of divalent silicon into metal-carbon and metal-hydrogen bonds

摘要

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 _2C _6H _3) with Me _2Zn, Me _3Al, H _3Al-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 _2Zn 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 _3Al, H _3Al-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.