Reactivity Tracers of the Hydrolysis of Fe(II)-Bis(salicylidene) Complexes: Initial-Transition States Analysis and Enhanced Impact of Tensides on the Kinetic Trends
作者:Lobna Abdel-Mohsen Ebaid Nassr
DOI:10.1002/kin.20970
日期:2016.2
The kinetics of the acid hydrolysis reaction of Fe(II)‐bis(salicylidene) complexes were followed under pseudo–first‐order conditions ([H+] >> [complex]) at 298 K. The ligands of the studied azomethine complexes were derived from the condensation of salicylaldehyde with different five α‐amino acids. The hydrolysis reactions were studied in acidic medium at different ratios (v/v) of aqua–organic mixtures
在拟一级条件([H + ] >> [配合物])下,于298 K下跟踪Fe(II)-双(水杨亚基)配合物的酸水解反应动力学。所研究的偶氮甲胺配合物的配体为来源于水杨醛与5种不同的α-氨基酸的缩合反应。在酸性介质中以不同比例(v / v)的水-有机混合物研究了水解反应。反应混合物的介电常数值的降低增强了反应的反应性。初始和过渡态(IS–TS)从水到混合溶剂的转移化学势是根据溶解度测量结果和动力学数据确定的。log k obs与1 / D的非线性图(介电常数的倒数)表明IS-TS的溶剂化对反应活性的影响。此外,在不同浓度的阳离子和阴离子表面活性剂存在下筛选酸水解反应。向反应混合物中添加表面活性剂可加速反应活性。将所获得的动力学数据被用于确定的值δ米Δ ģ #(在活化屏障的变化)对于所研究的络合物从转移“水到各种比例(V / V)的水-共-有机二元混合物”时从“水到含有不同[表面活性剂]的水”。发