作者:Brian G. Cox、Nguyen van Truong、Hermann Schneider
DOI:10.1039/f19848003285
日期:——
interact strongly with cations, the former pathway predominates for alkali-metal and alkaline-earth-metal cryptates. In poorly solvating media such as methanol and propylene carbonate, where dissociation rate constants are very low, bimolecular pathways make an important contribution to the overall exchange pathway. Exchange reactions of Ag+ cryptates show ligand-dependent rates and strong saturation
速率常数的金属穴状化合物络合物,MCry之间交换反应Ñ + 1,和一个自由穴状配体,惊魂2,已经在几种溶剂被确定。可以区分两种机理:MCry n + 1解离后通过游离金属阳离子进行反应,以及两个配体之间直接进行的双分子阳离子交换。在与阳离子强烈相互作用的溶剂(如水,二甲基亚砜和二甲基甲酰胺)中,前者的通道主要用于碱金属和碱土金属的盐酸盐。在离解速率常数非常低的溶剂化较差的介质(例如甲醇和碳酸亚丙酯)中,双分子途径对整个交换途径做出了重要贡献。Ag +隐窝的交换反应在甲醇和二甲基亚砜中均显示出依赖配体的速率和强烈的饱和效应。