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双核锇自由基配合物[Os_2Cp*_2(CO)_4]·^+的分离与结构表征

Isolation and structural characterization of a dinuclar osmium radical complex[Os_2Cp*_2(CO)_4]·^+
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摘要 为了探索金属与金属之间的化学键本质,对双核锇的配合物进行了单电子氧化,分离得到了一例双核锇的自由基阳离子配合物[Os_2Cp*_2(CO)_4]·^+,并进行了结构表征。通过对其进行电子顺磁共振光谱表征和理论计算,发现自旋密度主要位于配体上。单晶结构解析表明,双核锇的羰基化合物经过单电子后,金属间的键长几乎没有发生变化。同时在其与三苯甲基碳自由基阳离子的反应过程中,采取sp^3杂化的C—H键被活化。经推测,可能是通过electrochemical-chemical(EC)机理进行的。 Abstract： To explore the nature of metal-metal bonds, the carbonyl complex OS2〇 p ＊ 2 （CO）4 was carried out one-electron oxidation, and a radical cation of dinuclear osmium complex was isolated and structurally characterized. The EPR spectrum and theo-retical calculation indicate that the spin density mainly resides on ligands. The X-ray structure shows the change of metal-metal bond length is negligible upon one-electron oxidation, sp3 C-H bond activation was observed during the reaction of parent mole-cule with the trityl cation, which possibly occurs via an oxidative electrochemical-chemical （EC） mechanism.
作者 李淑昱 王兴勇 王新平
机构地区 南京大学化学化工学院 人工微结构科学与技术协同创新中心
出处 《中国科技论文》 CAS 北大核心 2016年第6期610-614,共5页 China Sciencepaper
基金 高等学校博士学科点专项科研基金资助项目(20110091120009)
关键词 配体 双核金属 锇 自由基阳离子 C—H键活化 ligands dinuclar metal diosmium radical cation C-H bond activation
分类号 O641.4 [理学—物理化学]
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参考文献35

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中国科技论文
2016年 第6期

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