A Terminal Fe^(III)-Oxo in a Tetranuclear Cluster: Effects of Distal Metal Centers on Structure and Reactivity
- Creators
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Reed, Christopher J.
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Agapie, Theodor
Abstract
Tetranuclear Fe clusters have been synthesized bearing a terminal Fe^(III)–oxo center stabilized by hydrogen-bonding interactions from pendant (tert-butylamino)pyrazolate ligands. This motif was supported in multiple Fe oxidation states, ranging from [Fe^(II)_2Fe^(III)_2] to [Fe^(III)_4]; two oxidation states were structurally characterized by single-crystal X-ray diffraction. The reactivity of the Fe^(III)–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.
Additional Information
© 2019 American Chemical Society. Received: March 22, 2019; Published: May 14, 2019. This research was supported by the NIH (R01-GM102687B) and the Dreyfus Teacher-Scholar Program (T.A.). C.J.R. thanks the Resnick Sustainability Institute at Caltech for a fellowship. We thank Dr. Mike Takase and Larry Henling for assistance with crystallography, Prof. Jonas Peters for use of his group's Mössbauer spectrometer, and the Dow Next Generation Educator Fund for instrumentation. The authors declare no competing financial interest.Attached Files
Accepted Version - nihms-1583112.pdf
Supplemental Material - ja9b03157_si_001.cif
Supplemental Material - ja9b03157_si_002.pdf
Files
Additional details
- Alternative title
- A Terminal FeIII-Oxo in a Tetranuclear Cluster: Effects of Distal Metal Centers on Structure and Reactivity
- PMCID
- PMC7207158
- Eprint ID
- 95500
- DOI
- 10.1021/jacs.9b03157
- Resolver ID
- CaltechAUTHORS:20190515-081947535
- NIH
- R01-GM102687B
- Camille and Henry Dreyfus Foundation
- Resnick Sustainability Institute
- Created
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2019-05-15Created from EPrint's datestamp field
- Updated
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2021-11-16Created from EPrint's last_modified field
- Caltech groups
- Resnick Sustainability Institute