High-valent iron complexes with tetraamido macrocyclic ligands: Structures, Mössbauer spectroscopy, and DFT calculations

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• 作者：Arani Chanda ; Delia-Laura Popescu ; Filipe Tiago de Oliveira ; Emile L. Bominaar ; Alexander D. Ryabov ; Eckard Mü ; nck and Terrence J. Collins
• 关键词：Fe(IV) complexes ; TAML complexes ; Mö ; ssbauer spectroscopy ; DFT calculations ; Green chemistry
• 刊名：Journal of Inorganic Biochemistry
• 出版年：2006
• 出版时间：April 2006
• 年：2006
• 卷：100
• 期：4
• 页码：606-619
• 全文大小：752 K

文摘

Iron complexes of tetraamido macrocyclic ligands (TAML) are unique synthetic oxidation catalysts. In general, the central Fe^III ion (S = 3/2) is surrounded by four, almost planar, deprotonated amide-N σ-donors although the full suite with new generation systems includes some substitution of amides with related donor functionalities. Oxidation under different conditions affords a variety of high-valent forms of iron–TAMLs. This review provides a summary and discussion of structural and spectroscopic features of complexes oxidized by one equivalent above the ferric state. These comprise Fe^IV–TAML high spin (S = 2) and intermediate spin (S = 1) systems, wherein the oxidation equivalent can be taken from the metal (Fe^IV) or the ligand (TAML radical-cation Fe^III), and coupled spin (S = 0) systems of μ-oxoiron(IV) dimers. The discussion is principally based on data obtained by X-ray crystallography, Mössbauer spectroscopy, and density functional theory calculations.