双核锇自由基配合物[Os2Cp*2(CO)4] •+的分离与结构表征
Isolation and structural characterization of a dinuclar osmium radical complex [Os2Cp*2(CO)4] ?+
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[Os2Cp*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sp3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。
o explore the nature of metal-metal bonds, the carbonyl complex Os2Cp*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 theoretical 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 molecule with the trityl cation, which possibly occurs via an oxidative electrochemical-chemical (EC) mechanism.
王新平、王兴勇、李淑昱
化学晶体学
配体双核金属锇自由基阳离子-H键活化
ligandsdinuclar metaldiosmiumradical cationC–H bond activation
王新平,王兴勇,李淑昱.双核锇自由基配合物[Os2Cp*2(CO)4] •+的分离与结构表征[EB/OL].(2017-05-11)[2025-08-16].http://www.paper.edu.cn/releasepaper/content/201705-708.点此复制
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