A Terminal FeIII–Oxo in a Tetranuclear Cluster: Effects of Distal Metal Centers on Structure and Reactivity
- 14 May 2019
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 141 (24), 9479-9484
- https://doi.org/10.1021/jacs.9b03157
Abstract
Tetranuclear Fe clusters have been synthesized bearing a terminal FeIII–oxo center stabilized by hydrogen-bonding interactions from pendant (tert-butylamino)pyrazolate ligands. This motif was supported in multiple Fe oxidation states, ranging from [FeII2FeIII2] to [FeIII4]; two oxidation states were structurally characterized by single-crystal X-ray diffraction. The reactivity of the FeIII–oxo center in proton-coupled electron transfer with X–H (X = C, O) bonds of various strengths was studied in conjunction with analysis of thermodynamic square schemes of the cluster oxidation states. These results demonstrate the important role of distal metal centers in modulating the reactivity of a terminal metal–oxo.Keywords
Funding Information
- Camille and Henry Dreyfus Foundation
- Resnick Sustainability Institute for Science, Energy and Sustainability, California Institute of Technology
- National Institute of General Medical Sciences (R01-GM102687B)
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