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

Julian A. Rees †‡, Vlad Martin-Diaconescu †, Julie A. Kovacs *‡, and Serena DeBeer *†§

† Max-Planck-Institut für Chemische Energiekonversion, Stiftstrasse 34-36, Mülheim an der Ruhr D-45470, Germany

‡ Department of Chemistry, University of Washington, Box 351700, Seattle, Washington 98195-1700, United States

§ Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, United States

Inorg. Chem., Article ASAP

DOI: 10.1021/acs.inorgchem.5b00699

Publication Date (Web): June 10, 2015

*E-mail: kovacs@chem.washington.edu., *E-mail: serena.debeer@cec.mpg.de.

Synopsis

An X-ray absorption and emission spectroscopic study has provided fundamental insight into the structural and electronic considerations governing O−O bond activation in a peroxo-bridged dimeric Mn(III) complex. Tuning of the Mn Lewis acidity via a cis σ* interaction modulates the extent of peroxo π* bonding into the unoccupied Mn d orbitals. Accompanying DFT calculations highlight the applicability of valence-to-core XES to the study of small-molecule activation.

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 rationale for the metastability of this unique compound, as well as potential future ligand designs which may further promote or inhibit O–O bond scission. Finally, we have explored the potential of VtC XES as an element-selective probe of both the coordination mode and degree of activation of peroxomanganese adducts. The comparison of these results to a recent VtC XES study of iron-mediated dintrogen activation helps to illustrate the factors that may determine the success of this spectroscopic method for future studies of small-molecule activation at transition metal sites.

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