作者:M. W. Grant、R. H. Prince
DOI:10.1039/j19690001138
日期:——
kinetics of the 36Cl–-exchange reaction of a number of labile organo-silicon and -germanium chlorides of the type R3MCl have been studied in acetone–dioxan mixture with the aid of an automated flow–quench system. The reactivity of all substrates decreases with increasing length of the alkyl chain; steric effects are more important in the reactions with silicon chlorides than with those of germanium.
所述的动力学36氯-一些不稳定的有机硅和类型R的-germanium氯化物的-exchange反应3的MC1了研究,在丙酮-二恶烷混合物用自动流骤冷系统的帮助。所有底物的反应性都随着烷基链长度的增加而降低。与氯化硅的反应比与锗的反应更重要的是空间效应。苄基和2-苯乙基取代基显示出意外的高反应活性。载盐Li 36的动力学顺序对于R =正丁基和环己基(M = Si)和R =苯基(M = Ge),Cl是二分之一,但对于2-苯基乙基和苄基,其顺序是统一的:这些顺序是根据相对反应性来解释的离子对和自由离子。活化参数表明,与硅相比,锗的活化焓较低,但熵熵较大。