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Probing Hydrogen Bonding Interactions to Iron-Oxido/Hydroxido Units by 57 Fe Nuclear Resonance Vibrational Spectroscopy.


ABSTRACT: Hydrogen bonds (H-bonds) have been shown to modulate the chemical reactivities of iron centers in iron-containing dioxygen-activating enzymes and model complexes. However, few examples are available that investigate how systematic changes in intramolecular H-bonds within the secondary coordination sphere influence specific properties of iron intermediates, such as iron-oxido/hydroxido species. Here, we used 57 Fe nuclear resonance vibrational spectroscopy (NRVS) to probe the Fe-O/OH vibrations in a series of FeIII -hydroxido and FeIV/III -oxido complexes with varying H-bonding networks but having similar trigonal bipyramidal primary coordination spheres. The data show that even subtle changes in the H-bonds to the Fe-O/OH units result in significant changes in their vibrational frequencies, thus demonstrating the utility of NRVS in studying the effect of the secondary coordination sphere to the reactivities of iron complexes.

SUBMITTER: Weitz AC 

PROVIDER: S-EPMC6263813 | biostudies-literature | 2018 Dec

REPOSITORIES: biostudies-literature

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Probing Hydrogen Bonding Interactions to Iron-Oxido/Hydroxido Units by <sup>57</sup> Fe Nuclear Resonance Vibrational Spectroscopy.

Weitz Andrew C AC   Hill Ethan A EA   Oswald Victoria F VF   Bominaar Emile L EL   Borovik Andrew S AS   Hendrich Michael P MP   Guo Yisong Y  

Angewandte Chemie (International ed. in English) 20181114 49


Hydrogen bonds (H-bonds) have been shown to modulate the chemical reactivities of iron centers in iron-containing dioxygen-activating enzymes and model complexes. However, few examples are available that investigate how systematic changes in intramolecular H-bonds within the secondary coordination sphere influence specific properties of iron intermediates, such as iron-oxido/hydroxido species. Here, we used <sup>57</sup> Fe nuclear resonance vibrational spectroscopy (NRVS) to probe the Fe-O/OH v  ...[more]

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