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Title: Tris(triisopropylsilyl)silane and the generation of bis(triisopropylsilyl)silylene

Abstract

Tris(triisopropylsilyl)silane (iPr{sub 3}Si){sub 3}SiH has been synthesized and studied by X-rah and neutron diffraction. It possesses an unusual structure in which the four silicon atoms are nearly coplanar, {angle}Si-Si-Si = 118.41(5){degree}. The Si-H distance is found to have a normal value of 1.506(2) {angstrom}. Thermal and room-temperature photochemical decomposition of (iPr{sub 3}-Si){sub 3}SiH leads to the elimination of iPr{sub 3}SiH and the generation of bis(triisopropylsilyl)silylene, [(iPr{sub 3}Si){sub 2}Si:]. Reactions of (iPr{sub 3}Si){sub 2}Si: include precedented insertions into H-Si bonds and addition to the {pi}-bonds of olefins, alkyenes, and dienes. Despite theoretical predictions of a triplet ground state for [(iPr{sub 3}Si){sub 2}Si:], stereospecific addition to cis- and trans-2-butene was observed.

Authors:
; ;  [1]
  1. Washington Univ., Saint Louis, MO (United States). Dept. of Chemistry [and others
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY
Sponsoring Org.:
National Science Foundation, Washington, DC (United States); USDOE, Washington, DC (United States)
OSTI Identifier:
696631
DOE Contract Number:  
AC02-98CH10886
Resource Type:
Journal Article
Journal Name:
Organometallics
Additional Journal Information:
Journal Volume: 18; Journal Issue: 19; Other Information: PBD: 13 Sep 1999
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; SILANES; ORGANIC SILICON COMPOUNDS; PHOTOLYSIS; DECOMPOSITION; MOLECULAR STRUCTURE

Citation Formats

Gaspar, P.P., Beatty, A.M., and Chen, T. Tris(triisopropylsilyl)silane and the generation of bis(triisopropylsilyl)silylene. United States: N. p., 1999. Web. doi:10.1021/om990418+.
Gaspar, P.P., Beatty, A.M., & Chen, T. Tris(triisopropylsilyl)silane and the generation of bis(triisopropylsilyl)silylene. United States. doi:10.1021/om990418+.
Gaspar, P.P., Beatty, A.M., and Chen, T. Mon . "Tris(triisopropylsilyl)silane and the generation of bis(triisopropylsilyl)silylene". United States. doi:10.1021/om990418+.
@article{osti_696631,
title = {Tris(triisopropylsilyl)silane and the generation of bis(triisopropylsilyl)silylene},
author = {Gaspar, P.P. and Beatty, A.M. and Chen, T.},
abstractNote = {Tris(triisopropylsilyl)silane (iPr{sub 3}Si){sub 3}SiH has been synthesized and studied by X-rah and neutron diffraction. It possesses an unusual structure in which the four silicon atoms are nearly coplanar, {angle}Si-Si-Si = 118.41(5){degree}. The Si-H distance is found to have a normal value of 1.506(2) {angstrom}. Thermal and room-temperature photochemical decomposition of (iPr{sub 3}-Si){sub 3}SiH leads to the elimination of iPr{sub 3}SiH and the generation of bis(triisopropylsilyl)silylene, [(iPr{sub 3}Si){sub 2}Si:]. Reactions of (iPr{sub 3}Si){sub 2}Si: include precedented insertions into H-Si bonds and addition to the {pi}-bonds of olefins, alkyenes, and dienes. Despite theoretical predictions of a triplet ground state for [(iPr{sub 3}Si){sub 2}Si:], stereospecific addition to cis- and trans-2-butene was observed.},
doi = {10.1021/om990418+},
journal = {Organometallics},
number = 19,
volume = 18,
place = {United States},
year = {1999},
month = {9}
}