LAUSR

The reactions of amidinate silylene chloride LSi(:)Cl (L = PhC(NtBu)2) with TMS- and Ph-ethynyl lithium salts gave rise to silacycles 1 and 4, respectively. The formation of 1 and 4 may undergo cyclo-condensations of transient ethynylsilylene intermidiates and the activation of an amidinate backbone. The distinct structures of 1 and 4 may be derived from the different electronic or steric properties of ethynyl substituents, and their formation mechanisms were investigated by density functional theory (DFT) calculations. Moreover, a sequential reaction of LSi(:)Cl with BH3·SMe2 and TMSC≡CLi as well as a reaction of LSi(:)Cl with TMSC≡CLi under O2 exclusively obtained ethynylsilanes 2 and 3, respectively, which indicated that either blocking a lone pair of a Si(II) atom or oxidizing Si(II) to Si(IV) prevents the further conversion of ethynylsilylenes to silacycle 1. All products were characterized by NMR spectroscopy and X-ray crystallography.