物理化学学报 >> 1985, Vol. 1 >> Issue (03): 232-238.doi: 10.3866/PKU.WHXB19850307

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五齿环戊二烯(四齿环丁二烯)镍(Ⅰ)衍生络合阳离子[Ni(C5R5)(C4R′4)]+的电化学还原反应

丁廷桢; U·柯勒   

  1. 清华大学化学与化学工程系; 西德亚琛工业大学无机化学所
  • 收稿日期:1984-09-25 修回日期:1984-12-20 发布日期:1985-06-15

ELECTROCHEMICAL REDUCTION OF h5-CYCLOPENTADIENYL-h4-CYCLOBUTADIENE-NICKEL-CATIONS, Ni(h5-C5R5)(h4-C4R4′)+

Ding Tingzhen; Ulrich Koelle   

  1. Department of Chemistry and Chemical Engineering, Tsinghua University, Beijing; Institut fuur Anorganische Chemie der Technischen Hochschule Aachen
  • Received:1984-09-25 Revised:1984-12-20 Published:1985-06-15

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摘要： 用循环伏安法, 计时电位法和计时电流法, 在二氯甲烷、乙腈、四氢呋哺和丙瞵撑碳酸酯等不同溶剂中, 在铂电极上研究了五齿环戊二稀(四齿环丁二稀)镍(Ⅰ)夹心络合阳离子, Ni(h~5-C_5R_5)(h~4-C_4R'_4)~+, (R=H,CH_3,R'=CH_3,C_6H_5)的电化学行为。实验结果表明: 对于R=H, R'=C_6H_5; R=CH_3, R'=C_6H_5的镍络离子为单电子的可逆还原反应, 产物为“19价电子壳层”的镍中性络合物。但是, 对于R=H, R'=CH_3; R=CH_3, R'=CH_3的镍络离子则因伴随有化学后置反应-二聚化反应而为不可逆的电极反应, 电化学还原反应的可逆性在四氢呋喃中有减小的趋势。此外, 用电解的方法对还原反应产物作了进一步的研究, 并对二聚分子的结构式提出建议。

Abstract: Electrochemical reduction of nickel sandwich complex-cations Ni(h~5-C_5eR_5) (h~4-C_4R'_4)~+, where R=H, CH_3; R'=CH_3, C_6H_5 was investigated at a Pt-electrode by means of cyclic voltametry, chronopotentiometry and chronoamperometry in dichloromethane, acetonitrile, tetrahydrofuran and propylenecarbonate (PC). The reduction are reversible and single electron processes for the compounds with R=H, R'=C_6H_5; R=CH_3, R'=C_6H_5 and the products are characteristic of “19-electron” nickel complexes. The complex cations exhibit an irreversible processes with coupled chemical reaction when R=H, R′=CH_3; R=CH_3, R′=CH_3. The stability of the reduction products was investigated further by bulk electrolysis. The reversibility of the electrochemical reduction tend to be reduced in THF.