Octahedral Non-Heme Oxo and Non-Oxo Fe(IV) Complexes: An Experimental/Theoretical Comparison

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• 作者：John F. Berry ; Eckhard Bill ; Eberhard Bothe ; Frank Neese ; Karl Wieghardt
• 刊名：Journal of the American Chemical Society
• 出版年：2006
• 出版时间：October 18, 2006
• 年：2006
• 卷：128
• 期：41
• 页码：13515 - 13528
• 全文大小：443K
• 年卷期：v.128,no.41(October 18, 2006)
• ISSN：1520-5126

文摘

Electron-transfer series are described for three ferric complexes of the pentadentate ligand 4,8,11-trimethyl-1,4,8,11-tetraazacyclotetradecane-1-acetate (Me₃cyclam-acetate) with axial chloride, fluoride, andazide ligands. These complexes can all be reduced coulometrically to their Fe(II) analogs and oxidizedreversibly to the corresponding Fe(IV) species. The Fe(II), Fe(III), and Fe(IV) species have been studiedspectroscopically and their UV-vis, Mössbauer, EPR, and IR spectra are presented. The fluoro species[(Me₃cyclam-acetate)FeF]ⁿ⁺ (n = 0, 1, 2) have been studied computationally using density functional theory(DFT), and the electronic structure of the Fe(IV) dication [(Me₃cyclam-acetate)FeF]²⁺ is compared withthat of the isoelectronic Fe(IV) oxo cation [(Me₃cyclam-acetate)FeO]⁺; the different properties of the twospecies are mainly due to the significantly covalent Fe=O bonds in the latter.