Abstract
Photochemical reactions of phenyl-substituted digermoxanes, (Ph n Me 3- n Ge) 2O ( n = 1–3), and a cyclic germoxane, (Me 2GeO) 4, have been investigated by chemical trapping and laser flash-photolysis. On irradiation, phenylated digermoxanes undergo homolysis of the germanium—oxygen bond to give germyl radicals and germoxy radicals. In the presence of nonhalogenated solvents, these germyl radicals and gerrnoxy radicals couple to yield digermanes and digermyl peroxides, respectively. In polyhalomethanes (CCl 4, CHCl 3, and BrCCl 3), germyl radicals are converted to the corresponding halides by abstraction of a halogen atom. Germoxy radicals do not react with polyhalomethanes; they couple to produce digermyl peroxides which decompose to give either a pair of germoxy radicals or germyl radicals and germylperoxy radicals. Photolysis of a cyclic germoxane also results in cleavage of the germanim—oxygen bond.
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