Spectroscopic and computational studies of (mu-oxo)(mu-1,2-peroxo)diiron(III) complexes of relevance to nonheme diiron oxygenase intermediates |
| |
Authors: | Fiedler Adam T Shan Xiaopeng Mehn Mark P Kaizer József Torelli Stéphane Frisch Jonathan R Kodera Masahito Que Lawrence |
| |
Institution: | Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant Street S.E., Minneapolis, Minnesota 55455, USA. |
| |
Abstract: | With the goal of gaining insight into the structures of peroxo intermediates observed for oxygen-activating nonheme diiron enzymes, a series of metastable synthetic diiron(III)-peroxo complexes with Fe(III)(2)(mu-O)(mu-1,2-O(2))] cores has been characterized by X-ray absorption and resonance Raman spectroscopies, EXAFS analysis shows that this basic core structure gives rise to an Fe-Fe distance of approximately 3.15 A; the distance is decreased by 0.1 A upon introduction of an additional carboxylate bridge. In corresponding resonance Raman studies, vibrations arising from both the Fe-O-Fe and the Fe-O-O-Fe units can be observed. Importantly a linear correlation can be discerned between the nu(O-O) frequency of a complex and its Fe-Fe distance among the subset of complexes with Fe(III)(2)(mu-OR)(mu-1,2-O(2))] cores (R = H, alkyl, aryl, or no substituent). These experimental studies are complemented by a normal coordinate analysis and DFT calculations. |
| |
Keywords: | |
本文献已被 PubMed 等数据库收录! |
|