Spectroscopic and Reactivity Comparisons of a Pair of bTAML Complexes with Fe^V═O and Fe^IV═O Units.

ABSTRACT: In this report we compare the geometric and electronic structures and reactivities of [Fe^V(O)]^- and [Fe^IV(O)]^2- species supported by the same ancillary nonheme biuret tetraamido macrocyclic ligand (bTAML). Resonance Raman studies show that the Fe═O vibration of the [Fe^IV(O)]^2- complex 2 is at 798 cm^-1, compared to 862 cm^-1 for the corresponding [Fe^V(O)]^- species 3, a 64 cm^-1 frequency difference reasonably reproduced by density functional theory calculations. These values are, respectively, the lowest and the highest frequencies observed thus far for nonheme high-valent Fe═O complexes. Extended X-ray absorption fine structure analysis of 3 reveals an Fe═O bond length of

SUBMITTER: Pattanayak S 

PROVIDER: S-EPMC5908480 | biostudies-literature | 2017 Jun

REPOSITORIES: biostudies-literature