02090nas a2200193 4500008004100000245005500041210005300096260000800149300001600157490000700173520150800180100002401688700002601712700001501738700001701753700002401770700001901794856008301813 2019 eng d00a Synthesis and reactivity of a hypersilylsilylene 0 aSynthesis and reactivity of a hypersilylsilylene cAUG a10536-105420 v583 a

Stabilization of an amidinatosilylene with a bulky tris(trimethylsilyl)silyl substituent was realized with the preparation of PhC(NtBu)(2)Si{Si(SiMe3)(3)} (1) from PhC(NtBu)(2)SiHCl2 with K{Si(SiMe3)(3)} in more than 90% yield. The highly deshielded Si-29 NMR resonance (delta = 76.91 ppm) can be attributed to the absence of a pi-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) angstrom. 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.

1 aBisai, Milan, Kumar1 aSwamy, V., S. V. S. N1 aDas, Tamal1 aVanka, Kumar1 aGonnade, Rajesh, G.1 aSen, Sakya, S. uhttps://library.ncl.res.in/content/synthesis-and-reactivity-hypersilylsilylene