Synthesis and Properties of Di-π-[8]annulenecerium(IV), Cerocene
Synthesis and Properties of Di-π-[8]annulenecerium(IV), Cerocene
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二茂铁 Di-π-[8]annulenecerium(IV) 的合成与性能
DOI：
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发表时间：
2004
期刊：
影响因子：
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通讯作者：
J. Rigsbee
中科院分区：
文献类型：
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作者：
A. Streitwieser;S. Kinsley;C. Jenson;J. Rigsbee
报道了一种通过K[Ce(C8H8)2]与烯丙基溴反应合成二π-([8]轮烯)Ce(IV)的方法。也可以通过在四氢呋喃中氧化相应的CeO_3和银盐来制备Cerocenes，但这种反应的变化性更大。Cerocene只与UCl4缓慢反应生成铀新烯。在核磁共振时间尺度上，K[Ce(C8H8)2]与均三茂铁发生电子交换。电化学研究表明，Ce(C8H8)2-与Ce(C8H8)2-的氧化还原是可逆的，还原电位较低(−0.6V vs NHE)。相应的稀土盐K[Pr(C8H8)2]没有发生类似的可逆氧化；其循环伏安与K2[Yb(C8H8)2]的循环伏安进行了比较。均三茂铁的化学性质类似于二π-([8]轮烯)榄系元素(IV)化合物。
An efficient synthesis of di-π-([8]annulene)cerium(IV) (cerocene) is reported by the reaction of K[Ce(C8H8)2] with allyl bromide. Cerocenes can also be prepared by oxidation of the corrresponding cerates with silver iodide in THF, but this reaction is more variable. Cerocene reacts only slowly with UCl4 to give uranocene. K[Ce(C8H8)2] and cerocene undergo electron exchange on the NMR time scale. Electrochemical study of cerocene shows redox with the cerate ion, Ce(C8H8)2-, to be reversible with a relatively low reduction potential (−0.6 V vs NHE). The corresponding praeseodymium salt, K[Pr(C8H8)2], does not undergo comparable reversible oxidation; its cyclic voltammetry is compared with that of K2[Yb(C8H8)2]. The chemistry of cerocene resembles that of di-π-([8]annulene)actinide(IV) compounds.