51533-82-5Relevant academic research and scientific papers
Direct detection of methylphenylgermylene and 1,2-dimethyl-1,2- diphenyldigermene - Kinetic studies of their reactivities in solution
Leigh, William J.,Dumbrava, Ileana G.,Lollmahomed, Farahnaz
, p. 934 - 948 (2007/10/03)
Photolysis of 1,3,4-trimethyl-1-phenylgermacyclopent-3-ene (5) in hydrocarbon solvents containing isoprene, methanol, or acetic acid affords 2,3-dimethyl-1,3-butadiene (DMB) and the expected trapping products of methylphenylgermylene (GeMePh) in chemical yields exceeding 90%. The germylene has been detected in hexane solution by laser flash photolysis as a short-lived species (τ ～ 2 μs) exhibiting a UV-vis absorption spectrum centered at λmax = 490 nm. It decays with second-order kinetics and a rate constant close to the diffusion-controlled limit, with the concomitant growth of a second longer-lived transient (λmax = 420 nm) that is assigned to a mixture of (E)- and (Z)-1,2-dimethyl-1,2-diphenyldigermene (4). Absolute rate constants have been determined for the reactions of the germylene with primary and tertiary amines (n-BuNH2 and Et 3N, respectively), acetic acid (AcOH), a terminal alkyne and alkene, isoprene, DMB, CCl4, and the group 14 hydrides Et3SiH and Bu3SnH. GeMePh is slightly more reactive than GePh2 towards all the reagents studied in this work; both are significantly less reactive than GeMe2 toward the same substrates. Absolute rate constants for the reactions of 4 have also been measured or assigned upper limits in every case and are compared to previously reported values for tetraphenyl- and tetramethyl-digermene with the same reagents.
Photochemical Reactions of Aryl-Substituted Digermanes through a Pair of Organogermyl Radicals
Mochida, Kunio,Wakasa, Masanobu,Sakaguchi, Yoshio,Hayashi, Hisaharu
, p. 1889 - 1895 (2007/10/02)
The photochemical reactions of aryl-substituted digermanes were investigated by trapping experiments and a laser flash photolysis technique.The photolysis of phenylated digermanes resulted in germanium-germanium bond homolysis to give a pair of two germyl radicals.The germyl radicals abstracted a chlorine atom from carbon tetrachloride to give chlorogermanes.The pair of germyl radicals also underwent ipso-substitution, which was a precursor of the germylenes.The mechanism for the photochemistry of phenylated digermenes is discussed.
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.
ASSISTANCE NUCLEOPHILE DANS DES REACTIONS D'ORGANO-HALOGENO- ET -HALOGENO-HYDROGERMANES: GERMYLANIONS, GERMYLENES, DERIVES FONCTIONNELS DU GERMANIUM
Riviere, P.,Castel, A.,Satge, J.
, p. 123 - 136 (2007/10/02)
Substitution reactions of halogermanes under nucleophilic assistance of tertiary amines or diazo derivatives leading readily to various functional derivatives of germanium have been carried out.Dehydrohalogenation of acidic halohydrogemanes under nucleophilic assistance is a useful way to divalent species, and the germylenes formed are stabilized by complexation with the nucleophilic agent.The reactions proceed via intermediate halogermylanions which lead to the formation of more stable germylenes.The transient halogemylanions have been characterized by means of their nuclophilic additions to carbonyl derivatives.Nucleophilic substitutions of halogermanes using these germylanions lead to the formation of polygermanes.
