Journal
INORGANIC CHEMISTRY
Volume 53, Issue 19, Pages 10378-10385Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ic501462y
Keywords
-
Categories
Funding
- Max-Planck-Gesellschaft
- Alfred P. Sloan foundation
- National Science Foundation
- National Institutes of Health/National Institute of General Medical Sciences under NSF award [DMR-0936384]
Ask authors/readers for more resources
Transition-metal K beta X-ray emission spectroscopy (XES) is a developing technique that probes the occupied molecular orbitals of a metal complex. As an element-specific probe of metal centers, K beta XES is finding increasing applications in catalytic and, in particular, bioinorganic systems. For the continued development of XES as a probe of these complex systems, however, the full range of factors which contribute to XES spectral modulations must be explored. In this report, an investigation of a series of oxo-bridged iron dimers reveals that the intensity of valence-to-core features is sensitive to the Fe-O-Fe bond angle. The intensity of these features has a well-known dependence on metal-ligand bond distance, but a dependence upon bond angle has not previously been documented. Herein, we explore the angular dependence of valence-to-core XES features both experimentally and computationally. Taken together, these results show that, as the Fe-O-Fe angle decreases, the intensity of the K beta '' feature increases and that this effect is modulated by increasing amounts of Fe np mixing into the O 2s orbital at smaller bond angles. The relevance of these findings to the identification of oxygenated intermediates in bioinorganic systems is highlighted, with special emphasis given to the case of soluble methane monooxygenase.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available