Hydrogermylation of 1,3-dienes using nickel catalyst systems

Synthesis and Gas Phase Thermochemistry of Germanium-Containing Compounds

“…After 8 h, the solvent was removed in vacuo and the product purified by distillation, giving 68 (4.1 g, 27 mmol, 70%) as a clear liquid (b p. 131. 3,109.9, 33.25, 23.9; IR (neat, cm 1 ) 3333(br), 3083, 2947, 2883,1623,1419, 1290, 1050GC-MS (El): m/z 152 (M +2 , 7), 150 (M + , 7), 122 (80), 121 (19), 120 (84), 119 (18), 95 (8), 93 (8), 81 7, 80 (4), 79 (6), 72 (5), 71 (100), 69 (4), 53 (13), 51 (8); HRMS (El) m/z calcd for C 4 H 7 OBr 169.96803, found 169.96835.…”

Synthesis and gas phase thermochemistry of germanium-containing compounds

“…In the samples with toluene only a trace of allyltrimethylgermane was present, and in addition the amount of 1,5-hexadiene was reduced. Since toluene can intercept radicals, it seems clear that the production of both 1,5-hexadiene and allyltrimethylgermane (18) are the result of radical processes. Similar chain radical processes have been proposed to explain the byproducts of the pyrolysis of diallyldimethylsilane (2) and allyltrimethylsilane (5).…”

“…Tables 10 and 11 show the composition of the gaseous products from the thermal decomposition of tetrapropylgermane (18) and tetrabutylgermane (19) respectively. The observed major products of tetrapropylgermane (18) are propene, propane and hydrogen.…”

“…Pyrolysis of allyltrimethylgermane (18) in the presence of 2,3-dimethyl-1,3-butadiene. 168 Scheme 8.…”

“…The source of propene is not evident, since cyclopropane does not yield significant amounts of propene at the temperatures involved in the experiments. 18 Kinetic experiments undertaken in a static vessel over the temperature range of 416-478 °C were performed by Conlin. Using a steady state approximation for germylene, the following rate expression can be obtained, which describes the observed rate constant for the disappearance of 37.…”