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dc.contributor.authorAlemayehu, Abraham
dc.contributor.authorMccormick-Mcpherson, Laura J
dc.contributor.authorConradie, Jeanet
dc.contributor.authorGhosh, Abhik
dc.date.accessioned2022-03-30T05:41:56Z
dc.date.available2022-03-30T05:41:56Z
dc.date.issued2021-05-17
dc.description.abstractThe interaction of free-base triarylcorroles with Re<sub>2</sub>(CO)<sub>10</sub> in 1,2- dichlorobenzene in the presence of 2,6-lutidine at 180 °C under strict anerobic conditions afforded approximately 10% yields of rhenium corrole dimers. The compounds exhibited diamagnetic <sup>1</sup> H NMR spectra consistent with a metal−metal quadruple bond with a σ<sup>2</sup> π<sup>4</sup> δ<sup>2</sup> orbital occupancy. One of the compounds proved amenable to single-crystal X-ray structure determination, yielding a metal−metal distance of ∼2.24 Å, essentially identical to that in triple-bonded osmium corrole dimers. On the other hand, the electrochemical properties of Re and Os corrole dimers proved to be radically different. Thus, the reduction potentials of the Re corrole dimers are some 800 mV upshifted relative to those of their Os counterparts. Stated differently, the Re corrole dimers are dramatically easier to reduce, reflecting electron addition to δ* versus π* molecular orbitals for Re and Os corrole dimers, respectively. The data also imply electrochemical HOMO-LUMO gaps of only 1.0− 1.1 V for rhenium corrole dimers, compared with values of 1.85−1.90 V for their Os counterparts. These HOMO−LUMO gaps rank among the first such values reported for quadruple-bonded transition-metal dimers for any type of supporting ligand, porphyrin-type or not.en_US
dc.identifier.citationAlemayehu A, Mccormick-Mcpherson LJ, Conradie J, Ghosh A. Rhenium Corrole Dimers: Electrochemical Insights into the Nature of the Metal–Metal Quadruple Bond. Inorganic Chemistry. 2021;60:8315-8321en_US
dc.identifier.cristinIDFRIDAID 2013414
dc.identifier.doi10.1021/acs.inorgchem.1c00986
dc.identifier.issn0020-1669
dc.identifier.issn1520-510X
dc.identifier.urihttps://hdl.handle.net/10037/24636
dc.language.isoengen_US
dc.publisherACS Publicationsen_US
dc.relation.journalInorganic Chemistry
dc.rights.accessRightsopenAccessen_US
dc.rights.holderCopyright 2021 The Author(s)en_US
dc.titleRhenium Corrole Dimers: Electrochemical Insights into the Nature of the Metal–Metal Quadruple Bonden_US
dc.type.versionpublishedVersionen_US
dc.typeJournal articleen_US
dc.typeTidsskriftartikkelen_US
dc.typePeer revieweden_US


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