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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Acid-base equilibria of various oxidation states of aqua-ruthenium complexes with 1,10-phenanthroline-5,6-dione in aqueous media
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Acid-base equilibria of various oxidation states of aqua-ruthenium complexes with 1,10-phenanthroline-5,6-dione in aqueous media

机译：水性介质中水合钌与1,10-菲咯啉-5,6-二酮的各种氧化态的酸碱平衡

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摘要

Synthees and pH dependent electrochemcial properties of aqua-ruthenium (II)complexes,[Ru(trpy)(PDA-N,N')_-(OH_2)](ClO_4)_2([1](ClO)_4_2) and [Ru(trpy)(PD-N,N')(OH_2)](ClO_4)_29[2](ClO_4)_2)(trpy=2,2':6',2"-terpyridine,PDA=6-acetonyl-6-hydroxyl-1,10-phenanthroline-5-one,PD=1,10-phenanthrolien-5,6-dione)are presented.Treatment of [Ru(trpy)(PD-N,N')Cl](PF_6)with AgClO_4 in a mixed solvent of acetone and H_2O selectively produced the acetonyl-PD complex [1](ClO_4)_2,and th esimlar treatment in a mixed solvent of 2-methoxyethanol and H_2O gave the PD compelx[2](CloO_4)_2.The moleculr structures of both compelxes were determined by X-ray structural analysis.The proton dissocition constants of various oxidations state of [1]~(2+)and [2]~(2+) were evaluated by simulation of E_(1/2) values of those redox potentials depending on poH.The simulation revealed that the acetonyl-PD compelx [1]~(2+) underwent succesisve Ru(II)/Ru(III) and Ru(III)/Ru(IV) redox couples though the two redox reactosn were not separated in thecyclic voltammograms.the redox behavior of [2]~(2+) in H_2O is reasonably explained by not only the similar successive metla-centered redox reactiosn but also simultaneous two-electron quinone/catechol redox couple of the PD ligand including the contribution of hydration on a carbonyl carbon.
机译：钌（II）配合物[Ru（trpy）（PDA-N，N'）_-（OH_2）]（ClO_4）_2（[1]（ClO）_4_2）和[Ru]的合成和pH依赖的电化学性质（trpy）（PD-N，N'）（OH_2）]（ClO_4）_29 [2]（ClO_4）_2）（trpy = 2,2'：6'，2“-叔吡啶，PDA = 6-丙酮基-6 -羟基-1,10-菲咯啉-5-one，PD = 1,10-菲咯啉-5,6-二酮）的制备。[Ru（trpy）（PD-N，N'）Cl]（PF_6）的处理在丙酮和H_2O的混合溶剂中用AgClO_4选择性地生成丙酮基-PD配合物[1]（ClO_4）_2，然后在2-甲氧基乙醇和H_2O的混合溶剂中进行类似处理，得到PD化合物[2]（CloO_4）_2通过X射线结构分析确定两个共轭分子的分子结构。通过模拟E_（1）评估[1]〜（2+）和[2]〜（2+）各种氧化态的质子离解常数模拟结果表明，乙酰基-PD复合物[1]〜（2+）成功获得Ru（II）/ Ru（III）和Ru（III）/ Ru（IV）的值。氧化还原对虽然两个氧化还原反应是[2]〜（2+）在H_2O中的氧化还原行为不仅可以通过相似的连续的以甲基为中心的连续氧化还原反应进行合理解释，而且可以通过PD配体的同时双电子醌/邻苯二酚氧化还原对进行合理解释，包括水合对羰基碳的贡献。

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