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A Terminal Fe^(III)-Oxo in a Tetranuclear Cluster: Effects of Distal Metal Centers on Structure and Reactivity

Reed, Christopher J. and Agapie, Theodor (2019) A Terminal Fe^(III)-Oxo in a Tetranuclear Cluster: Effects of Distal Metal Centers on Structure and Reactivity. Journal of the American Chemical Society, 141 (24). pp. 9479-9484. ISSN 0002-7863. http://resolver.caltech.edu/CaltechAUTHORS:20190515-081947535

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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.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/jacs.9b03157DOIArticle
ORCID:
AuthorORCID
Reed, Christopher J.0000-0002-8774-5106
Agapie, Theodor0000-0002-9692-7614
Alternate Title:A Terminal FeIII-Oxo in a Tetranuclear Cluster: Effects of Distal Metal Centers on Structure and Reactivity
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.
Group:Resnick Sustainability Institute
Funders:
Funding AgencyGrant Number
NIHR01-GM102687B
Camille and Henry Dreyfus FoundationUNSPECIFIED
Resnick Sustainability InstituteUNSPECIFIED
Record Number:CaltechAUTHORS:20190515-081947535
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20190515-081947535
Official Citation:A Terminal FeIII–Oxo in a Tetranuclear Cluster: Effects of Distal Metal Centers on Structure and Reactivity. Christopher J. Reed and Theodor Agapie. Journal of the American Chemical Society 2019 141 (24), 9479-9484 DOI: 10.1021/jacs.9b03157
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:95500
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:15 May 2019 23:06
Last Modified:25 Jun 2019 18:10

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