Tris(triisopropylsilyl)silane (iPr(3)Si)(3)SiH 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, angle Si-Si-Si = 118.41(5)degrees. The Si-H distance is found to have a normal value of 1.506(2) Angstrom. Thermal and room-temperature photochemical decomposition of (iPr(3)-Si)(3)SiH leads to the elimination of iPr(3)SiH and the generation of bis(triisopropylsilyl)silylene, [(iPr(3)Si)(2)Si:]. Reactions of(iPr(3)Si)(2)Si: include precedented insertions into H-Si bonds and addition to the pi-bonds of olefins, alkynes, and dienes. Despite theoretical predictions of a triplet ground state for [(iPr(3)Si)(2)Si:], stereospecific addition to cis- and trans-2-butene was observed.
Tris(triisopropylsilyl)silane and the generation of bis (triisopropylsilyl)silylene / P. Gaspar, A. Beatty, T. Chen, T. Haile, D. Lei, W. Winchester, J. Braddock Wilking, N. Rath, W. Klooster, T. Koetzle, S. Mason, A. Albinati. - In: ORGANOMETALLICS. - ISSN 0276-7333. - 18:19(1999 Sep 13), pp. 3921-3932.
Tris(triisopropylsilyl)silane and the generation of bis (triisopropylsilyl)silylene
A. AlbinatiUltimo
1999
Abstract
Tris(triisopropylsilyl)silane (iPr(3)Si)(3)SiH 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, angle Si-Si-Si = 118.41(5)degrees. The Si-H distance is found to have a normal value of 1.506(2) Angstrom. Thermal and room-temperature photochemical decomposition of (iPr(3)-Si)(3)SiH leads to the elimination of iPr(3)SiH and the generation of bis(triisopropylsilyl)silylene, [(iPr(3)Si)(2)Si:]. Reactions of(iPr(3)Si)(2)Si: include precedented insertions into H-Si bonds and addition to the pi-bonds of olefins, alkynes, and dienes. Despite theoretical predictions of a triplet ground state for [(iPr(3)Si)(2)Si:], stereospecific addition to cis- and trans-2-butene was observed.File | Dimensione | Formato | |
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