- Laser flash photolysis studies of some dimethylgermylene precursors
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The laser flash photolysis of dodecamethylcyclohexagermane (1) and dimethylphenyl(trimethylsilyl)- germane (5), two known photochemical precursors to dimethylgermylene (GeMe2), has been reinvestigated. Laser flash photolysis of 1 in hexane solu
- Lollmahomed, Farahnaz,Leigh, William J.
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- New photochemical routes to germylenes and germenes and kinetic evidence concerning the germylene-diene addition mechanism
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Upon 254-nm irradiation of phenylbis(trimethylsilyl)germanes, there is competition between two germylene-forming reactions, the unexpected elimination of phenyltrimethylsilane and the elimination of hexamethyldisilane. Irradiation of a phenylmonosilylgermane PhGeMe2SiMe3 leads to predominant elimination of PhSiMe3, forming dimethylgermylene Me2Ge:, accompanied by migration of Me3Si to the ortho position of the phenyl ring, forming a germene. Laser flash photolysis of PhGeMe2SiMe3 is a convenient source of Me3Ge:, and rate constants are reported for Me2Ge: addition to a series of dienes and other substrates. The kinetic data are in accord with 1,2-addition as the dominant pathway for addition of Me2Ge: to 1,3-dienes.
- Bobbitt, Kevin L.,Maloney, Vincent M.,Gaspar, Peter P.
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p. 2772 - 2777
(2008/10/08)
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