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.
Laser Flash Photolysis Studies of Some Dimethylgermylene Precursors
作者:Farahnaz Lollmahomed、William J. Leigh
DOI:10.1021/om9000814
日期:2009.6.8
The laserflashphotolysis of dodecamethylcyclohexagermane (1) and dimethylphenyl(trimethylsilyl)germane (5), two known photochemical precursors to dimethylgermylene (GeMe2), has been reinvestigated. Laserflashphotolysis of 1 in hexane solution affords markedly different results than were reported in an earlier study of this compound in cyclohexane. The present study shows it to yield two primary
Reaction of Triorgano(Triorganogermyl)Silanes with Alkali-Metal Allyl Aicoholates
作者:Mikio Kabaki、Sumie Inoue、Yoshiro Sato
DOI:10.1080/00397919208055424
日期:1992.1
Reaction of the lithium alcoholates of 1-vinylcyclohexanol (2a), (+/-)-linalool (2b), and 1-octen-3-ol (2c) with (dimethylphenylgermyl)trimethylsilane (3a) gave selectively the corresponding allyldimethylphenylgermane derivatives (5a,c,e). Similar treatment with dimethylphenyl(trimethylgermyl)silane (3b) gave mixtures of the allyltrimethylgermanes (5b,d,f) and allyldimethylphenylsilanes (7b,d,f), whereas use of the potassium alcoholates afforded selectively 5b,d,f.
An alternative route to allylgermanes by the palladium-catalyzed reaction of germylsilanes with allylic halides
作者:Kazuyoshi Ono、Hisao Ishizuka、Taichi Nakano
DOI:10.1016/s0022-328x(99)00308-3
日期:1999.9
Pd(dba)(2) (bis(dibenzylideneacetone)palladium complex) effectively catalyzes the reaction of (dimethylphenylgermyl)trimethylsilane with 2-alkenyl halides to bring about metal-, regio- and stereoselective metathesis resulting in the formation of 2-alkenylphenylgermanes with good yields. On the other hand, the reaction of (chlorodimethylgermyl)trimethylsilane with 2-alkenyl halides is effected by a palladium-phosphine complex to give 2-alkenylchlorogermanes selectively. Germylation of 3,4-dichloro-1-butene with (dimethylphenylgermyl)trimethylsilane forms 1,4-bis(dimethylphenylgermyl)-2-butene with a high yield. (C) 1999 Elsevier Science S.A. All rights reserved.