2237-93-6Relevant articles and documents
FT-IR study of the gas-phase autoxidation of trimethylgermane
Harrison, Philip G.,Podesta, David M.
, p. 1569 - 1574 (1994)
The kinetics and mechanism of the autoxidation of trimethylgermane in the gas phase has been investigated in the temperature range 493-533 K using Fourier transform infrared spectroscopy. Over a wide molar ratio of reactants (Me3GeH:O2 ratio in the range (1:1)-(1:31)) the loss of Me3GeH follows second-order kinetics but is independent of oxygen abundance. The products of the reaction are hexamethyldigermoxane, Me3GeOGeMe3, and water. No other products are apparent. For a 1:10 Me3GeH:O2 molar ratio, second-order rate constants vary from 2.46 mol-1 dm3 s-1 at 493 K to 64.1 mol-1 dm3 s-1 at 533 K. The activation energy for the process is determined to be 190 ± 19 kJ mol-1. The proposed mechanism involves an initial abstraction of the hydridic hydrogen atom from germanium followed by the reaction of the trimethylgermyl radical thus formed with oxygen, giving the (trimethylgermyl)peroxyl radical. This radical is converted into trimethylgermyl hydroperoxide, Me3GeOOH, by further H-abstraction from Me3GeH and undergoes O-O bond fission to form (trimethylgermyl)oxyl and hydroxyl radicals. The radicals thus produced propagate the reaction by H-abstraction from Me3GeH, forming the intermediate Me3GeOH and water. Hexamethyldigermoxane is subsequently formed by self-condensation of two Me3GeOH molecules.
Synthesis of α-germyl and α-silylcarboxylic acids and selected electrochemical oxidations
Rakovshik, Anna,Shtelman, Alex V.,Becker, James Y.
, p. 13 - 19 (2012/06/17)
New α-germylcarboxylic acids, α-silyl-α-halocarboxylic and α-silyl-α-alkylcarboxylic acids including some known α-silyl(cycloalkyl)carboxylic acids have been prepared by different synthetic methods. The anodic oxidation in basic methanol of selected examp
Photochemical reactions of 2-(pentamethyldisilanyl)furan and 2-(pentamethyldigermanyl)furan. Formation of a radical pair
Mochida, Kunio,Kimijima, Kohichi,Wakasa, Masanobu,Hayashi, Hisaharu
, p. 101 - 108 (2007/10/02)
Photochemical reactions of 2-(pentamethyldisilanyl)furan and 2-(pentamethyldigermanyl)furan have been investigated by chemical trapping experiments and laser flash-photolysis.On irradiation, the furylated catenates of Group 14 elements undergo silicon-silicon ? bond and germanium-germanium ? bond homolysis to give a pair of silyl radicals and germyl radicals, respectively.In CCl4, these radicals are converted to the corresponding chlorides by abstraction of a chlorine atom.In nonhalogenated solvents (cyclohexane and other hydrocarbons), the silyl radical pair undergoes a disproportionation to give as main products a monosilane and a silene.The trimethylgermyl radical mainly couples at the ipso-position of the furyl group of the pairing radical to yield the corresponding diradical.This diradical undergoes elimination of a divalent species, dimethylgermylene, with concomitant formation of 2-(trimethylgermyl)furan. Key words: Photochemistry; Silanyl; Germanyl; Radical
