Synthesis and reactivity of a hypersilylsilylene

Title Synthesis and reactivity of a hypersilylsilylene
Publication TypeJournal Article
Year of Publication2019
AuthorsBisai, MKumar, Swamy, VSVSN, Das, T, Vanka, K, Gonnade, RG, Sen, SS
JournalInorganic chemistry
Volume58
Issue16
Pagination10536-10542
Date PublishedAUG
Type of ArticleArticle
Abstract

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.

DOI10.1021/acs.inorgchem.9b00418
Type of Journal (Indian or Foreign)

Foreign

Impact Factor (IF)

4.85

Divison category: 
Catalysis and Inorganic Chemistry
Physical and Materials Chemistry

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