Anodic Electrochemistry of Multiferrocenyl Phosphine and Phosphine Chalcogenide Complexes in Weakly Nucleophilic Electrolytes

Citations Over TimeTop 10% of 2004 papers

Abstract

The anodic electrochemistry of several compounds containing two or three ferrocenyl moieties linked by a phosphine or phosphine chalcogenide group has been studied in dichloromethane containing [NBu4][TFAB], where TFAB is the tetrakis(perfluoroaryl)borate anion, [B(C6F5)4]-. In two cases, namely [CpFe(C5H4)]3P (3) and [CpFe(C5H4)]2PO(Ph) (6), the first one-electron-oxidation product is stable on the cyclic voltammetric (CV) time scale and subsequent oxidations at more positive potentials are also observed. The oxidations of [CpFe(C5H4)]2PPh (2) and [CpFe(C5H4)]3PSe (7) are not reversible, and their monocations undergo follow-up reactions that are first-order and second-order, respectively, in the neutral compound. The results are consistent with a model in which the initial oxidation always involves a largely ferrocenyl-based HOMO which, nevertheless, has significant phosphine or phosphine chalcogenide character, allowing radical-type reactions, including dimerizations, at the linking group. The traditional nonaqueous supporting electrolyte anions such as [PF6]- and [BF4]- are shown to be responsible for many of the earlier difficulties in interpreting the anodic electrochemistry of this oft-studied class of compounds.

Related Papers

• → Solvent Properties of Dichloromethane. II. The Reactivity of Dichloromethane Toward Amines.(1984)46 cited
• → Solvent Properties of Dichloromethane. VI. Dielectric Properties of Electrolytes in Dichloromethane.(1987)28 cited
• Phosphine oxides, sulphides, selenides and tellurides(1992)
• Lipopolysaccharide로 자극된 RAW 264.7 세포와 마우스 귀부종 모델에 대한 참치 심장 Dichloromethane 분획물의 항염증 효과(2017)
• → ChemInform Abstract: SOLVENT PROPERTIES OF DICHLOROMETHANE. II. THE REACTIVITY OF DICHLOROMETHANE TOWARD AMINES(1985)