Steric and Electronic Factors That Control Two-Electron Processes between Metal Carbonyl Cations and Anions

Yueqian Zhen, William G. Feighery, Chung Kung Lai, Jim D. Atwood

研究成果: 雜誌貢獻期刊論文同行評審

44 引文 斯高帕斯(Scopus)

摘要

Reactions of metal carbonyl cations (Mn(CO)6+, Re(CO)6+, Mn(CO)4PPh3+, Mn(CO)4(PPh3)2+, Mn(CO)5PEt3+, Mn(CO)5PPh2Me+, Re(CO)5PPh3+, and CpFe(CO)3+) with metal carbonyl anions (Co(CO)3PPh3, Co(CO)4, Mn(CO)5, Mn(CO)4PPh3, Mn(CO)4PEt3, Mn(CO)4PPh2Me, Mn(CO)3(PPh3)2, CpFe(CO)2, Re(CO)5, and Re(CO)4PPh3) are reported. Peak potentials are reported for all ions, and nucleophilicities (as measured by reaction with Mel) are reported for the anions. Reaction of any metal carbonyl cation with any metal carbonyl anion leads ultimately to binuclear products, which are the thermodynamic products. The binuclear products are formed by a single-electron transfer. In over half of the reactions between metal carbonyl cations and anions, a two-electron change results in a new metal carbonyl cation and anion. The two-electron change may be considered mechanistically as a CO2+ transfer with the more nucleophilic of the two anions retaining the CO2+. The kinetic and thermodynamic driving forces and the suggested mechanism are examined.

原文???core.languages.en_GB???
頁(從 - 到)7832-7837
頁數6
期刊Journal of the American Chemical Society
111
發行號20
DOIs
出版狀態已出版 - 9月 1989

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