A range of nickel-group IVbcomplexes of the type π-C5H5(R3M)(L)Ni (R = halide, alkyl or aryl, M = Si, Ge, Sn, L = R3P, R3As, C6H11NC) are reported. With few exceptions they are air-stable in the solid state, but oxidise in solution. Monoalkyl- or aryl-ation of NiGeCl3 and NiSnCl3 can be achieved using Et4Pb or Ph2Hg; the products are less stable and more readily oxidised than the trihalo derivatives
solids. The complex (Ph3P)2Rh(H)Cl(GeEt3) loses Et3GeH on reaction with carbon monoxide or ethylene; with hydrogen chloride triethylchlorogermane is formed. Excess of HGeCl3 and (Ph3P)3RhCl give the phosphonium salt, [Ph3PH]3[Rh(GeCl3)6], and similar salts are formed by the reaction between HGeCl3 and RhCl3 in acid solution, e.g. [Me3NH]3[RhCl3(GeCl3)3]. Rhodium(I)–germanium complexes, (Ph3P)2(CO)Rh(GeCl3)
A novel photochemicaladdition of a germyl radical to the olefinic double bond was discovered when benzyltriethylgermane or dibenzyldiethylgermane was irradiated with a medium-pressure mercury lamp in the presence of olefins.
NOVEL PHOTOREARRANGEMENT OF 3-PHENYL-2-PROPENYLGERMANES
作者:Masanori Kobayashi、Michio Kobayashi
DOI:10.1246/cl.1986.385
日期:1986.3.5
3-Phenyl-2-propenylgermanes, R3GeCH2CH=CHPh (R=Me, Et, Pr, Bu, Ph) were found to rearrange to 1-phenyl-2-propenylgermanes, R3GeCH(Ph)CH=CH2 upon irradiation with low pressure mercury lamp in cyclohexane.
3-Phenyl-2-propenylgermanes, R3GeCH2CH=CHPh (R=Me, Et, Pr, Bu, Ph) 被发现在低压汞照射下重排为 1-phenyl-2-propenylgermanes, R3GeCH(Ph)CH=CH2环己烷中的灯。
NMR Spectra of Organogermanium Compounds. X. Syntheses,<sup>13</sup>C and<sup>73</sup>Ge NMR Spectra and Molecular Mechanics Calculations of Germacyclopentanes and Germacyclopentenes
Germacyclopentane, its 1-methyl, and 1,1-dimethyl derivatives together with some germacyclopentenes were prepared and their 13C and 73Ge NMR spectra were determined. Molecular mechanics calculations of germacyclopentanes indicate that the symmetric twist form is the most stable in contrast to cyclopentane where the envelop and twist forms have much the same energy. Though both 13C and 73Ge chemical shifts are less sensitive to the stereochemistry of the methyl group as compared with the corresponding germacyclohexanes, the spectroscopic results can be explained in terms of the structures as depicted by molecular mechanics calculations.