Reactions of Stable Amidinate Chlorosilylene and [1+4]-Oxidative Addition of N-Heterocyclic Silylene with N-Benzylideneaniline

The reaction of PhC(NtBu)(2)SiCl (L) with N2O afforded the trimer {PhC(NtBu)(2)Si(O)Cl}(3) (1), which contains a Si3O3 six-membered ring. In the molecular structure of 1, the PhC(NtBu)(2) moieties are arranged around the Si3O3 six-membered ring in a paddle-wheel fashion. Further the reaction of L with B(C6F5)(3) and 9-BBN (9-borobicyclo[3.3.1]nonane) yielded the chlorosilylene-boron adducts L center dot B(C6F5)(3) (2) and L center dot 9-BBN (3). The reaction ofCH{(C=CH2)(CMe)(2,6-iPr(2)C(6)H(3)N)(2)} Si (L') with N-benzylideneaniline resulted in 4, a [1+4]- rather than a [1+2]-cycloaddition product. Compounds 1-4 were characterized by elemental analyses and spectroscopic methods. The molecular structures of 1, 2, and 4 were established unequivocally by single-crystal X-ray structural analysis. The formation of products 1 and 4 was supported by DFT calculations.