Direct Time-Resolved Study of the Gas-Phase Reactions of Germylene with Ethyl- and Diethylgermane: Absolute Rate Constants, Temperature Dependences, and Mechanism
作者:Rosa Becerra、Sergey E. Boganov、Mikhail P. Egorov、Irina V. Krylova、Oleg M. Nefedov、Robin Walsh
DOI:10.1021/jp0661948
日期:2007.3.1
Time-resolved studies of germylene, GeH2, generated by the 193 nm laser flash photolysis of 3,4-dimethyl-1-germacyclopent-3-ene, have been carried out to obtain rate constants for its bimolecular reactions with ethyl- and diethylgermanes in the gas phase. The reactions were studied over the pressure range 1-100 Torr with SF6 as bath gas and at five temperatures in the range 297-564 K. Only slight pressure
进行了时间分辨的3,4-二甲基-1-germacyclopent-3-ene的193 nm激光闪光光解产生的亚甲基锗酸GeH2的研究,以求得其与乙基和二乙基锗烷的双分子反应的速率常数。气相。在1-6 Torr的压力范围内,以SF6作为熔池气体,并在297-564 K的五个温度下对反应进行了研究。GeH2+ EtGeH3(399、486和564 K)的压力依赖性很小。高压速率常数给出以下Arrhenius参数:对于GeH2 + EtGeH3,log A = -10.75 +/- 0.08,Ea = -6.7 +/- 0.6 kJ mol-1;对于GeH 2 + Et 2 GeH 2,log A = -10.68 +/- 0.11,Ea = -6.95 +/- 0.80 kJ mol-1。这些与298 K时快速,近碰撞控制的关联过程一致。RRKM建模计算大部分是:与观察到的GeH2 + EtG