enthalpy, and the binding stoichiometry all in a single experiment. For systems in which two equivalents of ligand were able to bind to the Pd center, the binding sites on each Pd center in solution showed a different thermodynamic affinity for the same ligand. Changes in binding modes between different phosphorus ligands were due to steric bulk and poor electron-donating ability of such ligands. Our results
我们研究了一系列
磷配体与模型化合物PdCl 2(solv)2的结合热力学。,其中溶剂溶剂是指使用等温滴定量热(ITC)的溶剂分子。ITC允许在单个实验中定量平衡结合常数,结合焓和结合
化学计量。对于其中两个当量的
配体能够结合到Pd中心的系统,溶液中每个Pd中心上的结合位点对同一
配体显示出不同的热力学亲和力。不同
磷配体之间结合模式的变化归因于这些
配体的空间体积和较弱的给电子能力。我们的结果表明,由于溶剂
重组,
配体结合受到强烈的焓驱动,这是本体溶剂中溶剂分子的重排以及溶剂化物种周围的溶剂分子的重排。