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

Journal Article · Mon Sep 13 04:00:00 EDT 1999 · Organometallics

DOI:https://doi.org/10.1021/om990418+· OSTI ID:696631

Gaspar, P P; Beatty, A M; Chen, T ^[1]

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1. Washington Univ., Saint Louis, MO (United States). Dept. of Chemistry; and others

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.

• Research Organization: Brookhaven National Laboratory (BNL), Upton, NY
• Sponsoring Organization: National Science Foundation, Washington, DC (United States); USDOE, Washington, DC (United States)
• DOE Contract Number: AC02-98CH10886
• OSTI ID: 696631
• Journal Information: Organometallics, Journal Name: Organometallics Journal Issue: 19 Vol. 18; ISSN ORGND7; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
DECOMPOSITION
MOLECULAR STRUCTURE
ORGANIC SILICON COMPOUNDS
PHOTOLYSIS
SILANES