该研究考察了锇ocene在二氯甲烷和丙酮腈中，不同电解质阴离子([BF4]⁻, [PF6]⁻, [B(C6F5)4]⁻)存在下的电化学氧化行为。结果表明，生成的锇ocene阳离子的反应活性显著受到电解质阴离子配位性质和溶剂给电子能力的影响。通过循环伏安法，首次检测到作为关键中间体的双阳离子[Cp2Os]²⁺的电化学特征，这有助于解释锇ocene的氧化伏安曲线模式。
摘要：
The electrochemical oxidation of osmocene was investigated in dichloromethane (DCM) and acetonitrile (MeCN) in the presence of various electrolyte anions ([BF4]−, [PF6]−, and [B(C6F5)4]−(TFAB)). The results showed that the reactivity of the electrogenerated osmocenium cation was dramatically affected by the coordinating properties of the electrolyte anion and the donor strength of the solvent. Cyclic voltammetry allowed the characterization of transient species and led to rationalization of some controversial mechanistic conclusions published before, which were in fact all correct, but referred to different conditions. Notably, the electrochemical signature of the dimer dication [Cp2Os]22+that appears as a crucial species to explain the voltammetric oxidative pattern of osmocene was detected for the first time.
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