134847-68-0Relevant academic research and scientific papers
New photochemical routes to germylenes and germenes and kinetic evidence concerning the germylene-diene addition mechanism
Bobbitt, Kevin L.,Maloney, Vincent M.,Gaspar, Peter P.
, p. 2772 - 2777 (2008/10/08)
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.
Photochemical reactions of aryl-substituted catenates of group 4B elements, PhMe2E-E'Me3 (E, E' = Si and Ge). Formation of a radical pair
Mochida, Kunio,Kikkawa, Haruhiko,Nakadaira, Yasuhiro
, p. 9 - 19 (2007/10/02)
Photochemical reactions of phenyl substituted catenates of group 4B elements, PhMe2E-E'Me3 (E, E' = Si and Ge) have been investigated by chemical trapping experiments and laser flash-photolysis.On irradiation, the phenylated group 4B catenate undergoes E-E' bond homolysis to give a pair of radicals (PhMe2E. and Me3E'.).In CCl4, these radicals are converted to the corresponding chlorides by abstraction of a chlorine atom.In a nonhalogenated solvent, the radical pair couples at the ipso-position of the phenyl group of the pairing radical (PhMe2E.) to yield the cor responding diradical.This undergoes either elimination of a divalent species (Me2E:) with concomitant formation of trimethylphenyl group 4B element PhMe3E') or intramolecular 1,2-group 4B element migration to yield group 4B metal-carbon double bonded species.The radical escapes from the solvent cage coupled to the metal atom of the radical to yield the dimetallic product.The reaction path observed is highly dependent on the nature of the group 4B element comprising the phenyl substituted catenate.
