Interactions of the "piano-stool" [ruthenium(II)(η(6) -arene)(quinolone)Cl](+) complexes with water; DFT computational study.

摘要: Full optimizations of stationary points along the reaction coordinate for hydration several quinolone Ru(II) half-sandwich complexes were performed in water environment using B3PW91/6-31+G(d)/PCM/UAKS method. The role diffuse functions (especially on oxygen) was found crucial correct geometries coordinate. Single-point (SP) calculations at B3LYP/6-311++G(2df,2pd)/DPCM/saled-UAKS level. In first part, two possible mechanisms-associative and dissociative compared. It that mechanism process is kinetically slightly preferred. Another important conclusion concerns channels. substitution chloride ligand (abbreviated text as dechlorination reaction) represents energetically most feasible pathway. second part same explored reactivity comparison Ru(II)-complexes with derivatives nalidixic acid: cinoxacin, ofloxacin, (thio)nalidixic acid. about four orders magnitude faster a basic solution compared to neutral/acidic cinoxacin acid reactive former latter environments, respectively. all cases endergonic; nevertheless endergonicity substantially lower (by ∼6 kcal/mol) environment. © 2016 Wiley Periodicals, Inc.