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Effects of the μ4-bridging atom in a tetranuclear iron cluster on the activation of nitric oxide

Reed, Christopher and Agapie, Theodor (2016) Effects of the μ4-bridging atom in a tetranuclear iron cluster on the activation of nitric oxide. In: 251st American Chemical Society National Meeting & Exposition, March 13-17, 2016, San Diego, CA. http://resolver.caltech.edu/CaltechAUTHORS:20160414-095853543

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Abstract

A series of tetrairon μ_4-fluoride clusters, [LFe_3F(PhPz)_3Fe][OTf]_n (n=1-3), was synthesized using the previously reported 1,3,5- triarylbenzene framework, a multinucleating ligand contg. pyridine and alkoxide donors, which bind three of the four metal centers. These three metal sites contain six-coordinate iron atoms. 3-phenyl-pyrazolate ligands (PhPz) bridge the triiron core to a four-coordinate, site-differentiated iron center. These clusters have notably different redox properties than the closely related μ_4-oxo analogs, [LFe_3O(PhPz)_3Fe][OTf]_n (n=0-3). While for [LFe_3O(PhPz)_3Fe][OTf]_2 three reversible redox events are obsd. at -1.73 V (vs. Fc /Fc+), -0.72 V, and +0.02 V (Fe^(II)_4 Fe^(II)Fe^(III)_3), only two redox events are obsd. for the fluoride-bridged cluster, [LFe_3F(PhPz)_3Fe][OTf], at -0.52 V (Fe^(II)_4 /Fe^(II)_3Fe^(III)) and +0.17 V, (Fe^(II)_3Fe^(III)/Fe^(II)_2 Fe^(III)_2). Each redox state of the fluoridebridged clusters, [LFe_3F(PhPz)_3Fe][OTf]_n (n=1-3), was isolated and further investigated through spectroscopy and X-ray diffraction. These studies reveal that all of the oxidn. state changes occur exclusively at one of the six- coordinate iron sites in the triiron core. Treatment of the above complexes with nitric oxide (NO) results in clusters with ν_(N-O) (1823 and 1842 cm^(-1)) higher than the corresponding oxo-bridged clusters of the same oxidn. states. The effects of the interstitial atom on small mol. activation will be discussed.


Item Type:Conference or Workshop Item (Paper)
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http://www.acs.org/content/acs/en/meetings/spring-2016.htmlOrganizationConference Website
ORCID:
AuthorORCID
Agapie, Theodor0000-0002-9692-7614
Additional Information:© 2016 American Chemical Society.
Record Number:CaltechAUTHORS:20160414-095853543
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20160414-095853543
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:66164
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:14 Apr 2016 17:09
Last Modified:05 May 2017 19:48

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