X-ray Absorption and Emission Study of Dioxygen Activation by a Small-Molecule Manganese Complex.

ABSTRACT: Manganese K-edge X-ray absorption (XAS) and Kβ emission (XES) spectroscopies were used to investigate the factors contributing to O-O bond activation in a small-molecule system. The recent structural characterization of a metastable peroxo-bridged dimeric Mn(III)2 complex derived from dioxygen has provided the first opportunity to obtain X-ray spectroscopic data on this type of species. Ground state and time-dependent density functional theory calculations have provided further insight into the nature of the transitions in XAS pre-edge and valence-to-core (VtC) XES spectral regions. An experimentally validated electronic structure description has also enabled the determination of structural and electronic factors that govern peroxo bond activation, and have allowed us to propose both a rat

SUBMITTER: Rees JA 

PROVIDER: S-EPMC4494871 | biostudies-literature | 2015 Jul

REPOSITORIES: biostudies-literature