Mn K-edge X-ray absorption studies of mononuclear Mn(III)-hydroxo complexes.

Mn K-edge X-ray absorption spectroscopy experiments were performed on the solid- and solution-phase samples of [MnII (dpaqR )](OTf) (R=H, Me) and [MnIII (OH)(dpaqR )](OTf). The extended X-ray absorption fine structure (EXAFS) data show distinct differences between the MnII and MnIII -OH complexes, with fits providing metric parameters in excellent agreement with values from X-ray crystallography and density functional theory (DFT) computations. Evaluation of the EXAFS data for solid-phase [MnIII (OH)(dpaq)](OTf) resolved a short Mn-OH bond distance of 1.79 Å; however, the short trans-amide nitrogen bond of the supporting ligand precluded the resolution of the Mn-OH bond distance in the corresponding solution-phase sample and for both [MnIII (OH)(dpaqMe )](OTf) samples. The edge energy also increases by approximately 2 eV from the MnII to the MnIII -OH complexes. Experimental pre-edge analysis shows the MnII complexes to have pre-edge areas comparable to the MnIII -OH complexes, despite the presence of the relatively short Mn-OH distance. Time-dependent density functional theory (TD-DFT) computations illustrate that Mn 3d-4p mixing, a primary contributor to pre-edge intensities, decreases by ~ 0.3% from the MnII to MnIII -OH complexes, which accounts for the very similar pre-edge areas. Collectively, this work shows that combined EXAFS and XANES analysis has great potential for identification of reactive MnIII -OH intermediates, such as those proposed in enzyme active sites.