期刊
COORDINATION CHEMISTRY REVIEWS
卷 257, 期 2, 页码 459-472出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/j.ccr.2012.06.024
关键词
X-ray absorption spectroscopy; Metal K-edge; Electronic structure; Bioinorganic chemistry; Transition metal-dioxygen complexes
资金
- Department of Energy, Office of Basic Energy Sciences
- National Institutes of Health, National Center for Research Resources, Biomedical Technology Program
- Department of Energy, Office of Biological and Environmental Research
- National Center for Research Resources (NCRR), a component of the National Institutes of Health (NIH) [P41 RR001209]
Metal K-edge X-ray absorption spectroscopy (XAS) has been extensively applied to bioinorganic chemistry to obtain geometric structure information on metalloprotein and biomimetic model complex active sites by analyzing the higher energy extended X-ray absorption fine structure (EXAFS) region of the spectrum. In recent years, focus has been on developing methodologies to interpret the lower energy K-pre-edge and rising-edge regions (XANES) and using it for electronic structure determination in complex bioinorganic systems. In this review, the evolution and progress of 3d-transition metal K-pre-edge and rising-edge methodology development is presented with particular focus on applications to bioinorganic systems. Applications to biomimetic transition metal-O-2 intermediates (M = Fe, Co. Ni and Cu) are reviewed, which demonstrate the power of the method as an electronic structure determination technique and its impact in understanding the role of supporting ligands in tuning the electronic configuration of transition metal-O-2 systems. (C) 2012 Elsevier B.V. All rights reserved.
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