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氢键“二聚体中的二聚体”中的混合价态。

Mixed valency in hydrogen bonded 'dimers of dimers'.

机构信息

Department of Chemistry, University of Sheffield, Sheffield, S3 7HF, UK.

出版信息

J Am Chem Soc. 2013 Feb 6;135(5):1723-6. doi: 10.1021/ja312176x. Epub 2013 Jan 27.

Abstract

Dimolybdenum quadruply bonded compounds containing a pendant lactam functional group form self-complementary hydrogen bonded 'dimers of dimers' in the solid-state and CH(2)Cl(2) solutions. Electrochemical studies in CH(2)Cl(2) show two consecutive one-electron redox processes corresponding to oxidation of the Mo(2)(4+) cores. Spectroelectrochemical studies on the 'dimers of dimers' show no evidence of intervalence charge transfer bands in the mixed valence radical cations formed by one-electron oxidation, indicating that they are examples of proton-coupled mixed valency.

摘要

含有悬垂内酰胺官能团的二钼四重键化合物在固态和 CH(2)Cl(2)溶液中形成自互补氢键“二聚体的二聚体”。CH(2)Cl(2)中的电化学研究表明,存在两个连续的单电子氧化还原过程,对应于 Mo(2)(4+)核的氧化。“二聚体的二聚体”的光谱电化学研究表明,在单电子氧化形成的混合价自由基阳离子中没有观察到价间电荷转移带,表明它们是质子耦合混合价的实例。

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