Tris(triisopropylsilyl)silane and the Generation of Bis(triisopropylsilyl)silylene
1999; American Chemical Society; Volume: 18; Issue: 19 Linguagem: Inglês
10.1021/om990418+
ISSN1520-6041
AutoresPeter P. Gaspar, A.M. Beatty, Tongqian Chen, Tesfamichael Haile, Deqing Lei, William R. Winchester, Janet Braddock‐Wilking, Nigam P. Rath, Wim T. Klooster, Thomas F. Koetzle, Sax A. Mason, Alberto Albinati,
Tópico(s)Organometallic Complex Synthesis and Catalysis
ResumoTris(triisopropylsilyl)silane (iPr3Si)3SiH has been synthesized and studied by X-ray and neutron diffraction. It possesses an unusual structure in which the four silicon atoms are nearly coplanar, ∠Si−Si−Si = 118.41(5)°. The Si−H distance is found to have a normal value of 1.506(2) A. Thermal and room-temperature photochemical decomposition of (iPr3Si)3SiH leads to the elimination of iPr3SiH and the generation of bis(triisopropylsilyl)silylene, [(iPr3Si)2Si:]. Reactions of (iPr3Si)2Si: include precedented insertions into H−Si bonds and addition to the π-bonds of olefins, alkynes, and dienes. Despite theoretical predictions of a triplet ground state for [(iPr3Si)2Si:], stereospecific addition to cis- and trans-2-butene was observed.
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