Investigation of the interaction of gold(III)-alkyldiamine complexes with l-histidine and imidazole ligands by ~1H and ~(13)C NMR, and UV spectrophotometry

摘要

Reactions of Au(III)-alkyldiamine complex with l-histidine and imidazole were carried out and monitored time-dependant by ~1H and ~(13)C NMR. Kinetics for the [Au(en)Cl_2]~+ reaction with l-histidine was determined by initial rate method at constant pH and 25 °C using UV-Vis absorption technique, and found to be first order with respect to each component, with a pseudo second order rate constant of 39 ± 3 M~(-1) s~(-1). Reaction rates of l-histidine and imidazole reactions with the [Au(en)Cl_2]~+ complex was found to be strongly dependant on pD. The pD also has profound effect on the stability of the complex. It was observed that concurrent redox reactions also take place in solution in which Au(III) is reduced to metallic Au(0), while l-histidine and imidazole are oxidized to oxy and hydroxyl products. The optimization of the structure of [(His)Au(en)]~(3+) complex was carried out by gaussian03 at the RB3LYP level that showed a distorted square pyramid with the histidine carboxyl group at the pyramid top.