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dc.contributor.authorHopmann, Kathrin H.
dc.contributor.authorConradie, Jeanet
dc.contributor.authorTangen, Espen
dc.contributor.authorTonzetich, Zachary John
dc.contributor.authorLippard, Stephen J.
dc.contributor.authorGhosh, Abhik
dc.date.accessioned2016-08-15T18:57:40Z
dc.date.available2016-08-15T18:57:40Z
dc.date.issued2015-07
dc.date.submitted2015-04
dc.identifier.issn0020-1669
dc.identifier.issn1520-510X
dc.identifier.urihttp://hdl.handle.net/1721.1/103917
dc.description.abstractA density functional theory (DFT) study of {CoNO}[superscript 8] cobalt nitrosyl complexes containing the [n,n]tropocoronand ligand (TC-n,n) has revealed a sharp reduction of singlet–triplet gaps as the structures change from near-square-pyramidal (for n = 3) to trigonal-bipyramidal with an equatorial NO (for n = 5, 6). An experimental reinvestigation of [Co(TC-3,3)(NO)] has confirmed that it is not paramagnetic, as originally reported, but diamagnetic, like all other {CoNO}[superscript 8] complexes. Furthermore, DFT calculations indicate a substantial singlet–triplet gap of about half an eV or higher for this complex. At the other end of the series, low-energy, thermally accessible triplet states are predicted for [Co(TC-6,6)(NO)]. Enhanced triplet-state reactivity may well provide a partial explanation for the failure to isolate this compound as a stable species.en_US
dc.description.sponsorshipResearch Council of Norwayen_US
dc.description.sponsorshipSouth African National Research Foundationen_US
dc.description.sponsorshipNational Institutes of Health (U.S.) (Postdoctoral Fellowship, 1 F32 GM082031-03)en_US
dc.language.isoen_US
dc.publisherAmerican Chemical Society (ACS)en_US
dc.relation.isversionofhttp://dx.doi.org/10.1021/acs.inorgchem.5b00901en_US
dc.rightsArticle is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.en_US
dc.sourceProf. Lippard via Erja Kajosaloen_US
dc.titleSinglet–Triplet Gaps of Cobalt Nitrosyls: Insights from Tropocoronand Complexesen_US
dc.typeArticleen_US
dc.identifier.citationHopmann, Kathrin H., Jeanet Conradie, Espen Tangen, Zachary J. Tonzetich, Stephen J. Lippard, and Abhik Ghosh. “Singlet–Triplet Gaps of Cobalt Nitrosyls: Insights from Tropocoronand Complexes.” Inorg. Chem. 54, no. 15 (August 3, 2015): 7362–7367.en_US
dc.contributor.departmentMassachusetts Institute of Technology. Department of Chemistryen_US
dc.contributor.approverLippard, Stephen J.en_US
dc.contributor.mitauthorTonzetich, Zachary Johnen_US
dc.contributor.mitauthorLippard, Stephen J.en_US
dc.relation.journalInorganic Chemistryen_US
dc.eprint.versionOriginal manuscripten_US
dc.type.urihttp://purl.org/eprint/type/JournalArticleen_US
eprint.statushttp://purl.org/eprint/status/NonPeerRevieweden_US
dspace.orderedauthorsHopmann, Kathrin H.; Conradie, Jeanet; Tangen, Espen; Tonzetich, Zachary J.; Lippard, Stephen J.; Ghosh, Abhiken_US
dspace.embargo.termsNen_US
dc.identifier.orcidhttps://orcid.org/0000-0002-2693-4982
mit.licensePUBLISHER_POLICYen_US


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