Synthesis and Reactivity of a Hypersilylsilylene

Abstract

Stabilization of an amidinatosilylene with a bulky tris(trimethylsilyl)silyl substituent was realized with the preparation of PhC(NtBu)₂Si{Si(SiMe₃)₃} (1) from PhC(NtBu)₂SiHCl₂ with K{Si(SiMe₃)₃} in more than 90% yield. The highly deshielded ²⁹Si NMR resonance (δ = 76.91 ppm) can be attributed to the absence of a π-donating substituent. The molecular structure of 1 shows a trigonal-planar geometry around the Si^II center with a Si^II-Si^IV bond length of 2.4339(13) Å. A series of reactions of 1 with Me₃NO, S, Se, and Te were performed. While siloxane derivatives (2 and 3) are obtained from reactions with Me₃NO, silachalcogenones (4-6) are formed with other chalcogens. The presence of Si═E (E = S, Se, and Te) bonds in 4-6 have been confirmed by single-crystal X-ray studies. Silaoxirane (7) formation was observed when 1 was treated with acetone, demonstrating the importance of the tris(trimethylsilyl)silyl group to kinetically and thermodynamically protect the silaoxirane derivative with less bulky substituents on the C atom.