UNUSUAL ELECTRON-TRANSFER PROCESSES INVOLVING ELECTRON-RICH AND ELECTRON-DEFICIENT METALLOCENES
UNUSUAL ELECTRON-TRANSFER PROCESSES INVOLVING ELECTRON-RICH AND ELECTRON-DEFICIENT METALLOCENES
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DOI：
10.1021/ja00463a066
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发表时间：
1977-01-01
影响因子：
15
通讯作者：
GEIGER, WE
中科院分区：
文献类型：
--
作者：
HOLLOWAY, JDL;BOWDEN, WL;GEIGER, WE
Cp2Cr的电子转移反应似乎是三种金属中最简单的。被报道。在THF或CH3CN中，Cp2Cr都经历了电化学可逆氧化生成Cp2Cr+和还原为CpzCr-的过程，如图1所示。再色系阳离子的盐，如Cp2CrI，是众所周知的9，阳离子可能保留对称共面环结构1。铬二茂的还原更有趣，对于Cp2Cr的阴离子，像除Co， 8,10·11外的所有其他金属二茂一样，以前没有报道过。这种还原的CV测量表明，阴离子对尚未确定的产物进行了后续反应，但CV峰高以及体积库仑测量表明，THF涉及一个单电子过程。在溶剂放电前，CP2V被降低（ca. 3v）。极谱和CV数据证实了钒二世阴离子可逆的单电子变化，与CpaCr呈等电子态。阴离子足够稳定，可以用慢CV监测，但尚未进行批量电解。
The electron-transfer reactions of Cp2Cr appear to be the simplest of the three metals. being reported. In either THF or CH3CN, Cp2Cr undergoes an electrochemically reversible oxidation to Cp2Cr+ and reduction to CpzCr-, as shown by CV (Figure 1). Salts of the chromocene cation, such as Cp2CrI, are well known, 9 and the cation probably retains the symmetric coplanar ring structure 1. The reduction of chromocene is more interesting, for the anion of Cp2Cr, like all other metallocenes except Co, 8, 10· 11 has not been previously reported. CV mea-surements of this reduction show· that the anion undergoes follow-up reactionsto as yet unspecified products, but the CV peak heights, as well as bulk coulometry measurements, show that a one-electron process is involved in THF.CP2V is reduced just before solvent discharge (ca.—3 V). Polarographic and CV data are consistent with a reversible one-electron change to givethe vanadocene anion, a species isoelectronic with CpaCr. The anion is stable enough to be monitored by slow CV, but no bulk electrolyseshave been performed as yet.