Mixed Valence Properties in Ferrocenyl-Based Bimetallic FeCp−Indenyl−MLn Complexes: Effect of the MLn Group

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• 作者：Saverio Santi ; Christian Durante ; Alessandro Donoli ; Annalisa Bisello ; Laura Orian ; Alberto Ceccon ; Laura Crociani ; Franco Benetollo
• 刊名：Organometallics
• 出版年：2009
• 出版时间：June 22, 2009
• 年：2009
• 卷：28
• 期：12
• 页码：3319-3326
• 全文大小：214K
• 年卷期：v.28,no.12(June 22, 2009)
• ISSN：1520-6041

文摘

A series of ferrocenyl-based complexes of general structure [η⁵-(2-ferrocenyl)indenyl]ML_n [ML_n = RuCp*, FeCp, IrCOD, Mn(CO)₃, and Cr(CO)₂NO] were synthesized with the aim of tuning the effect of the nature of the second metal group ML_n on the magnitude of the metal−metal electronic coupling in their mixed valence ions generated by electrochemical oxidation. The electronic interaction was probed by determining different and independent physical properties, the potential splitting in the cyclic voltammograms, and the IT bands in the near-IR spectra, which were rationalized in the framework of Marcus−Hush theory and at the quantum chemistry level by the density functional theory and TD density functional theory methods. On the basis of the obtained results, we were able to establish a trend based on the magnitude of the Fe−M electron transfer parameters H_ab and α ranging from weakly to moderately coupled mixed valence ions.