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Characterization of a High‐Spin Non‐Heme {FeNO} 8 Complex: Implications for the Reactivity of Iron Nitroxyl Species in Biology
dc.contributor.authorSpeelman, Amy L.en_US
dc.contributor.authorLehnert, Nicolaien_US
dc.date.accessioned2013-12-04T18:58:10Z
dc.date.available2015-01-05T13:54:43Zen_US
dc.date.issued2013-11-18en_US
dc.identifier.citationSpeelman, Amy L.; Lehnert, Nicolai (2013). "Characterization of a High‐Spin Non‐Heme {FeNO} 8 Complex: Implications for the Reactivity of Iron Nitroxyl Species in Biology ." Angewandte Chemie International Edition 52(47): 12283-12287.en_US
dc.identifier.issn1433-7851en_US
dc.identifier.issn1521-3773en_US
dc.identifier.urihttps://hdl.handle.net/2027.42/101872
dc.publisherWILEY‐VCH Verlagen_US
dc.subject.otherReductionen_US
dc.subject.otherBioinorganic Chemistryen_US
dc.subject.otherNitrogen Oxidesen_US
dc.subject.otherNitroxyl Complexesen_US
dc.subject.otherNon‐Heme Ironen_US
dc.titleCharacterization of a High‐Spin Non‐Heme {FeNO} 8 Complex: Implications for the Reactivity of Iron Nitroxyl Species in Biologyen_US
dc.typeArticleen_US
dc.rights.robotsIndexNoFollowen_US
dc.subject.hlbsecondlevelChemistryen_US
dc.subject.hlbtoplevelScienceen_US
dc.description.peerreviewedPeer Revieweden_US
dc.contributor.affiliationumDepartment of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, MI 48109 (USA)en_US
dc.description.bitstreamurlhttp://deepblue.lib.umich.edu/bitstream/2027.42/101872/1/12283_ftp.pdf
dc.description.bitstreamurlhttp://deepblue.lib.umich.edu/bitstream/2027.42/101872/2/anie_201305291_sm_miscellaneous_information.pdf
dc.identifier.doi10.1002/anie.201305291en_US
dc.identifier.sourceAngewandte Chemie International Editionen_US
dc.identifier.citedreferenceExperimental details for the acquisition of crystal data and structure refinement can be found in the Supporting Information. CCDC 945365 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.en_US
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dc.identifier.citedreferenceAs noted previously, [10a] the large τ  value (>1) presumably arises from the 0.364 Å displacement of the Fe center from the mean plane defined by the equatorial nitrogen atoms.en_US
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dc.identifier.citedreferenceThe parent complex [Fe(TMG 3 tren)(CH 3 CN)] 2+ shows only an irreversible reductive event at approximately −2.5 V versus ferrocene, [10c] which indicates that the reduction of 1 is not ligand‐based. This conclusion is supported by DFT calculations, which show only a small change in spin density on the ligand in 2 as compared to 1 (see Table S3 in the Supporting Information). Rather, the splitting in the ligand bands is indicative of changes in the covalency of the iron–TMG 3 tren unit.en_US
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dc.identifier.citedreferenceNo experimental p K a  values for biological {FeHNO} 8 ‐type complexes have been reported; however, DFT calculations suggest that 2 is less basic than the corresponding low‐spin (heme) complexes (see the Supporting Information).en_US
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dc.owningcollnameInterdisciplinary and Peer-Reviewed


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