Magnetic circular dichroism and computational study of mononuclear and dinuclear iron(IV) complexes.

ABSTRACT: High-valent iron(IV)-oxo species are key intermediates in the catalytic cycles of a range of O₂-activating iron enzymes. This work presents a detailed study of the electronic structures of mononuclear ([Fe^IV(O)(L)(NCMe)]²⁺, 1, L = tris(3,5-dimethyl-4-methoxylpyridyl-2-methyl)amine) and dinuclear ([(L)Fe^IV(O)(μ-O)Fe^IV(OH)(L)]³⁺, 2) iron(IV) complexes using absorption (ABS), magnetic circular dichroism (MCD) spectroscopy and wave-function-based quantum chemical calculations. For complex 1, the experimental MCD spectra at 2-10 K are dominated by a broad positive C-term band between 12000 and 18000 cm^-1. As the temperature increases up to ~20 K, this feature is gradually replaced by a deriv

SUBMITTER: Ye S 

PROVIDER: S-EPMC4583211 | biostudies-literature | 2015 May

REPOSITORIES: biostudies-literature