Iron corrolates: Unambiguous chloroiron(III) (corrolate)2− π-cation radicals

摘要: The structures, electron configurations, magnetic susceptibilities, spectroscopic properties, molecular orbital energies and spin density distributions, redox properties reactivities of iron corrolates having chloride, phenyl, pyridine, NO other ligands are reviewed. It is shown that with one very strong donor ligand such as phenyl anion the configuration metal d(4)S=1 Fe(IV) coordinated to a (corrolate)(3-) anion, while weaker chloride or halide, d(5)S=3/2 Fe(III) (corrolate)(2-.) pi-cation radical, antiferromagnetic coupling between corrolate radical electron. Many these complexes have been studied by electrochemical techniques rich reactivity, in most cases involving two 1-electron oxidations reductions, it not possible tell, from shapes cyclic voltammetric waves, whether added removed macrocycle; often infrared, UV-Vis, EPR spectroscopy can provide this information. (1)H (13)C NMR methods useful delineating state pattern distribution listed above, would also be expected case for recently-reported formal Fe(V)O corrolate, if complex were stable enough characterization spectroscopy. Iron, manganese chromium oxidized iodosylbenzene common oxidants used previously metalloporphyrinates effect efficient oxidation substrates. Whether "resting state" form complexes, generally [FeCl(Corr)], actually has Fe(IV)(Corr)(3-) Fe(III)(Corr)(2-.) relevant high-valent reactivity complex.