XANES evidence against a manganyl species in the S3 state of the oxygen-evolving complex

被引:55
作者
Weng, TC
Hsieh, WY
Uffelman, ES
Gordon-Wylie, SW
Collins, TJ
Pecoraro, VL [1 ]
Penner-Hahn, JE
机构
[1] Univ Michigan, Dept Chem, Ann Arbor, MI 48109 USA
[2] Univ Michigan, Div Biophys Res, Ann Arbor, MI 48109 USA
[3] Carnegie Mellon Univ, Dept Chem, Pittsburgh, PA 15213 USA
关键词
D O I
10.1021/ja0494104
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Manganyl Mn=O species have been suggested as possible intermediates in photosynthetic water oxidation and as the reactive species in asymmetric olefin epoxidation. The first X-ray absorption spectrum for a MnV=O complex is reported. Comparison of the EXAFS data for Na[MnV=O(HMPAB) with those for lower-valent Mn complexes suggests that EXAFS measurements and edge-energy measurements are unlikely to have sufficient sensitivity to reliably reflect the presence of Mn=O species. In contrast, the preedge transition for Na[MnV=O(HMPAB) is 4-fold more intense than the most intense preedge transition observed for nonmanganyl complexes. This increase in intensity is shown to be sufficiently sensitive to allow detection of a manganyl species if it isformed. These data together with published data for the photosynthetic oxygen-evolving complex provide strong evidence against the presence of manganyl Mn=O species in the oxygen-evolving complex through the S3 state. Copyright © 2004 American Chemical Society.
引用
收藏
页码:8070 / 8071
页数:2
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