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Tetranuclear Fe Clusters with a Varied Interstitial Ligand: Effects on the Structure, Redox Properties, and Nitric Oxide Activation

Reed, Christopher J. and Agapie, Theodor (2017) Tetranuclear Fe Clusters with a Varied Interstitial Ligand: Effects on the Structure, Redox Properties, and Nitric Oxide Activation. Inorganic Chemistry, 56 (21). pp. 13360-13367. ISSN 0020-1669. PMCID PMC6277142. http://resolver.caltech.edu/CaltechAUTHORS:20171020-132701117

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Abstract

A new series of tetranuclear Fe clusters displaying an interstitial μ_4-F ligand was prepared for a comparison to previously reported μ_4-O analogues. With a single nitric oxide (NO) coordinated as a reporter of small-molecule activation, the μ_4-F clusters were characterized in five redox states, from Fe^(II)_3{FeNO}^8 to Fe^(III)_3{FeNO}^7, with NO stretching frequencies ranging from 1680 to 1855 cm^(–1), respectively. Despite accessing more reduced states with an F– bridge, a two-electron reduction of the distal Fe centers is necessary for the μ_4-F clusters to activate NO to the same degree as the μ_4-O system; consequently, NO reactivity is observed at more positive potentials with μ_4-O than μ_4-F. Moreover, the μ_4-O ligand better translates redox changes of remote metal centers to diatomic ligand activation. The implication for biological active sites is that the higher-charge bridging ligand is more effective in tuning cluster properties, including the involvement of remote metal centers, for small-molecule activation.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.inorgchem.7b02114DOIArticle
http://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.7b02114PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/acs.inorgchem.7b02114PublisherSupporting Information
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6277142PubMed CentralArticle
ORCID:
AuthorORCID
Agapie, Theodor0000-0002-9692-7614
Alternate Title:Tetranuclear Iron Clusters with A Varied Interstitial Ligand: Effects On Structure, Redox Properties, and Nitric Oxide Activation
Additional Information:© 2017 American Chemical Society. Received: August 17, 2017. Publication Date (Web): October 20, 2017. This research was supported by the NIH (Grant R01-GM102687B) and the Dreyfus Teacher–Scholar Program (to T.A.). C.J.R. thanks the Resnick Sustainability Institute at Caltech for a fellowship. We thank Mike Takase and Larry Henling for assistance with crystallography and Jonas Peters for use of his laboratory’s Mössbauer spectrometer. C.J.R. is grateful to Graham de Ruiter and Niklas Thompson for insightful discussions. 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
PubMed Central ID:PMC6277142
Record Number:CaltechAUTHORS:20171020-132701117
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20171020-132701117
Official Citation:Tetranuclear Fe Clusters with a Varied Interstitial Ligand: Effects on the Structure, Redox Properties, and Nitric Oxide Activation. Christopher J. Reed and Theodor Agapie. Inorganic Chemistry 2017 56 (21), 13360-13367. DOI: 10.1021/acs.inorgchem.7b02114
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:82539
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:20 Oct 2017 20:34
Last Modified:05 Dec 2018 17:22

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