title: Photochemistry of cyclic trisilanes: "spring-loaded" precursors to methylphenylsilylene.
abstract: 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 that 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 (lambda(max)=270, 505 nm) and absolute rate constants for its reaction with methanol, triethylsilane, a terminal alkene, alkyne, and two aliphatic dienes at 25 degrees C are reported.
authors.affiliation: Department of Chemistry, McMaster University, 1280 Main Street West, Hamilton, ON L8S 4M1 (Canada), Fax: (+1) 905-522-2509.
authors.forename: Andrey G
authors.initials: AG
authors.lastname: Moiseev
authors.affiliation: Department of Chemistry, McMaster University, 1280 Main Street West, Hamilton, ON L8S 4M1 (Canada), Fax: (+1) 905-522-2509.
authors.forename: Eugénie
authors.initials: E
authors.lastname: Coulais
authors.affiliation: Department of Chemistry, McMaster University, 1280 Main Street West, Hamilton, ON L8S 4M1 (Canada), Fax: (+1) 905-522-2509.
authors.forename: William J
authors.initials: WJ
authors.lastname: Leigh