Synthesis, properties, and reactions of a series of stable dialkyl-substituted silicon-chalcogen doubly bonded compounds

Takeaki Iwamoto, Katsuhiro Sato, Shintaro Ishida, Chizuko Kabuto, Mitsuo Kira

Research output: Contribution to journalArticlepeer-review

99 Citations (Scopus)

Abstract

The first dialkyl-substituted silicon-chalcogen doubly bonded compounds [R2Si=X; R2 = 1,1,4,4-tetrakis(trimethylsilyl)butane-1,4- diyl, X = S (4), Se (54), and Te (6)] were synthesized by the reactions of an isolable dialkylsilylene R2Si: (3) with phosphine sulfide, elemental selenium, and elemental tellurium, respectively. Systematic changes of characteristics of silicon-chalcogen double bonds are elucidated by X-ray analysis, UV-vis spectroscopy, and DFT calculations. In the solid state, the unsaturated silicon atom in 4-6 adopts planar geometry and the extent of the shortening of Si=X double bonds from the corresponding Si-X single bonds decreases in the order 4 > 5 > 6. In the absorption spectra of 4-6, π → π* transition bands are observed distinctly in addition to n → π* transition bands. Both the n → π* and π → π* transitions are red-shifted in the order 4 < 5 < 6, and the difference between the energies of the two transitions is kept almost constant among 4-6. The tendency is explained using the qualitative perturbation theory and is reproduced by the DFT calculations for model silanechalcogenones. Addition reactions of water, methanol, and isoprene to 4-6 are reported.

Original languageEnglish
Pages (from-to)16914-16920
Number of pages7
JournalJournal of the American Chemical Society
Volume128
Issue number51
DOIs
Publication statusPublished - 2006 Dec 27

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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