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Photochemistry of Cyclic Trisilanes: “Spring‐Loaded” Precursors to Methylphenylsilylene
Author(s) -
Moiseev Andrey G.,
Coulais Eugénie,
Leigh William J.
Publication year - 2009
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200901249
Subject(s) - spring (device) , photochemistry , chemistry , engineering , structural engineering
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 ( λ max =270, 505 nm) and absolute rate constants for its reaction with methanol, triethylsilane, a terminal alkene, alkyne, and two aliphatic dienes at 25 °C are reported.