title: High-valent iron complexes with tetraamido macrocyclic ligands: structures, Mössbauer spectroscopy, and DFT calculations.
abstract: 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 sigma-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 mu-oxoiron(IV) dimers. The discussion is principally based on data obtained by X-ray crystallography, Mössbauer spectroscopy, and density functional theory calculations.
authors.affiliation: Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, PA 15213, USA.
authors.forename: Arani
authors.initials: A
authors.lastname: Chanda
authors.forename: Delia-Laura
authors.initials: DL
authors.lastname: Popescu
authors.forename: Filipe
authors.initials: F
authors.lastname: Tiago de Oliveira
authors.forename: Emile L
authors.initials: EL
authors.lastname: Bominaar
authors.forename: Alexander D
authors.initials: AD
authors.lastname: Ryabov
authors.forename: Eckard
authors.initials: E
authors.lastname: Münck
authors.forename: Terrence J
authors.initials: TJ
authors.lastname: Collins
mesh_terms: D007501:Iron / Q000737:chemistry*; D008024:Ligands; D047028:Macrocyclic Compounds / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D010084:Oxidation-Reduction; D015204:Spectroscopy, Mossbauer; D013329:Structure-Activity Relationship
chemical_list: D008024:Ligands; D047028:Macrocyclic Compounds; C066317:ferryl iron; D007501:Iron