Chem. Eur. J., 15, 8485-8491 (2009).

© Wiley-Interscience.

The Photochemistry of Cyclic Trisilanes. “Spring-Loaded” Precursors to Methylphenylsilylene.

Andrey G. Moiseev, Eugénie Coulais, and William J. Leigh*

Contribution from the Department of Chemistry, McMaster University, 1280 Main Street West, Hamilton, ON Canada L8S 4M1.

Two new cyclic trisilanes containing a SiMePh moiety in the central position have been synthesized, and their photochemistries studied by steady state and laser flash photolysis methods. The yield of the transient silylene SiMePh increases at the expense of the corresponding cyclic silene derivative (formed by photochemical 1,3-silyl migration into the phenyl ring) as the ring size is decreased from 7 to 6, facilitating the direct detection of the silylene by laser flash photolysis. The UV/vis spectrum of SiMePh in hexanes solution (λmax = 270, 505 nm) and absolute rate constants for its reaction with methanol, triethylsilane, a terminal alkene, alkyne, and two aliphatic dienes at 25 oC are reported.

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