Characterization of the successive one-electron oxidation products of the dicobalt fulvalenediyl (Fv) compound Co2Fv(CO)4 and its phosphine-substituted product
Characterization of the successive one-electron oxidation products of the dicobalt fulvalenediyl (Fv) compound Co2Fv(CO)4 and its phosphine-substituted product
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二钴富瓦烯二基(Fv)化合物Co2Fv(CO)4及其膦取代产物的连续单电子氧化产物的表征
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发表时间：
2008
期刊：
影响因子：
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通讯作者：
W. Geiger
中科院分区：
文献类型：
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作者：
A. Nafady;W. Geiger
研究了Co2Fv(CO) 4,1在含[NBu4][TFAB] （TFAB = [B(C6F5)4]−）的二氯甲烷中以阴离子为载体的阳极氧化反应。伏安法、安培法、库伦法和原位光谱电化学方法表明，在快速、扩散控制的过程中，1通过两个单电子步骤被氧化为1+ (E1/2 = 0.06 V)和12+ (E1/2 = 0.51 V)，没有证据表明产物在玻碳电极上吸附。而中性化合物具有两种金属的跨体结构，单位1+的IR和ESR光谱最好解释为产生于具有Co - Co键的顺体结构。ESR数据分析表明，1+的SOMO在金属和配体上有明显的离域。1/1+/12+电子转移系列的离散单电子反应与类似的6族和8族苯丙二烯配合物的直接双电子反应形成鲜明对比。自由基阳离子1+经历…的快速取代。
The anodic oxidation of Co2Fv(CO)4, 1, has been studied in dichloromethane containing [NBu4][TFAB] (TFAB = [B(C6F5)4]−) as the supporting electrolyte anion. Voltammetric, amperometric, coulometric, and in situ spectroelectrochemical methods showed that 1 is oxidized in two one-electron steps to 1+ (E1/2 = 0.06 V) and 12+ (E1/2 = 0.51 V) in fast, diffusion-controlled processes without evidence of product adsorption at glassy carbon electrodes. Whereas the neutral compound has a transoid configuration of the two metals, IR and ESR spectra of the monocation 1+ are best interpreted as arising from a cisoid structure with a Co−Co bond. Analysis of the ESR data suggests that the SOMO of 1+ is significantly delocalized over the metal and ligand moieties. The discrete one-electron reactions of the 1/1+/12+ electron-transfer series stand in contrast to the direct two-electron processes observed for analogous group 6 and group 8 dileptic fulvalenediyl complexes. The radical cation 1+ undergoes rapid substitution of...