Iron(III, IV, V)-oxo complexes studied by nuclear resonance vibrational spectroscopy

Content Provider	Semantic Scholar
Author	Guo, Yisong Weitz, Andrew C. Hendrich, Michael P.
Copyright Year	2017
Abstract	High-valent iron-oxo (FeIV=O, FeV=O) species have been identified as the key reactive intermediate to carry out numerous oxidative transformations in biology, which include hydroxylation, halogenation, desaturation, epoxidation, endoperoxidation, ring expansion and ring contraction. Some of these transformations are key chemical steps in many biological pathways, such as DNA/RNA repair, gene regulation, O2 sensing, and natural product biosynthesis. Very recently, high-valent iron-oxo species have also been hypothesized to be involved in water splitting in iron-based synthetic catalysts. In order to design synthetic catalysts that can harvest the strong oxidizing power demonstrated by iron-oxo species in a controlled fashion, it is necessary to obtain a thorough molecular level description of the bonding interactions in the Fe=O moiety and its interaction with the supporting ligand. In the past decades, experimental and theoretical efforts have brought significant progress on the understandings of electronic structure and reactivity relation in iron-oxo species. However, detailed spectroscopic studies on Fe=O moieties that are in different oxidation states but supported by similar ligand systems are rare. By using synchrotron radiation based 57Fe nuclear resonance vibrational spectroscopy (NRVS, nuclear resonance inelastic x-ray scattering, NRIXS) together with 16O/18O isotope labeling, we have revealed the vibrational signatures of Fe=O moieties in three different oxidation state (FeIII, FeIV and FeV). Based on these vibrational data, we are able to extract the electronic effects of the iron oxidation state and the supporting ligand to the bonding interaction and thus the intrinsic reactivity of the Fe=O moiety.
File Format	PDF HTM / HTML
DOI	10.1107/S2053273317084741
Volume Number	73
Alternate Webpage(s)	http://journals.iucr.org/a/issues/2017/a2/00/a56196/a56196.pdf
Alternate Webpage(s)	http://www.iucr2017.org/abstract/myaccount/pdf/iucr2017-abstract-9285c01677fb99eedb41d44e2e2d34ee.pdf
Alternate Webpage(s)	https://doi.org/10.1107/S2053273317084741
Language	English
Access Restriction	Open
Content Type	Text
Resource Type	Article