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dc.contributor.authorChan S.-C.-
dc.contributor.authorAng Z.Z.-
dc.contributor.authorGupta, Puneet-
dc.contributor.authorGanguly R.-
dc.contributor.authorLi Y.-
dc.contributor.authorYe S.-
dc.contributor.authorEngland J.-
dc.date.accessioned2022-02-22T11:39:04Z-
dc.date.available2022-02-22T11:39:04Z-
dc.date.issued2020-
dc.identifier.citationInorganic Chemistry, 59(6): 4118-4128-
dc.identifier.issn201669-
dc.identifier.other32101411-
dc.identifier.urihttps://doi.org/10.1021/acs.inorgchem.0c00153-
dc.identifier.urihttp://repository.iitr.ac.in/handle/123456789/20728-
dc.description.abstractCarbodicarbenes (CDCs) possess two lone pairs of electrons on their central carbone C atom (Ccarbone). Coordination to a transition metal via a σ bond leaves one pair of electrons with appropriate symmetry for πdonation to the metal. However, the high energy of the latter also renders the CDC ligand potentially redox-active. Herein, we explore these alternatives in the redox series [Cr(L)2]n+ and [Co(L)2]n+ (n = 2-5), where L is a tridentate ligand comprised of a central CDC and two flanking pyridine donors. To this end, all members of both redox series were synthesized and their electronic structures were investigated by using a combination of 1H NMR, Evans' NMR, IR, UV-vis, and EPR spectroscopies, SQUID magnetometry, X-ray crystallography, and density functional theory studies. Whereas [CoII(L)2]2+ is a straightforward low-spin (S = 1/2) cobalt(II) complex, the corresponding chromium complex was found to feature an electronic structure that is intermediate between the two limiting resonance forms [CrIII(L•-)(L)]2+ and [CrII(L)2]2+. In the case of the tri-, tetra-, and pentacationic complexes, the qualitatively identical electronic structures [MIII(L)2]3+, [MIII(L•+)(L)]4+, and [MIII(L•+)2]5+ were observed for both metals. Thus, the metal ions retain a 3+ oxidation state throughout, and the higher redox states contain oxidized ligands. The majority of the unpaired spin on the cation radical ligands was calculated to be localized in π-symmetry orbitals on the coordinated Ccarbone atoms. Analogous behavior was previously reported for the corresponding iron redox series and, as such, redox noninnocence in oxidized CDC and, more broadly, carbone complexes is likely widely accessible. © 2020 American Chemical Society.-
dc.language.isoen_US-
dc.publisherAmerican Chemical Society-
dc.relation.ispartofInorganic Chemistry-
dc.titleCarbodicarbene Ligand Redox Noninnocence in Highly Oxidized Chromium and Cobalt Complexes-
dc.typeArticle-
dc.scopusid36697633900-
dc.scopusid57212246724-
dc.scopusid57215231630-
dc.scopusid55675224139-
dc.scopusid57202988209-
dc.scopusid8346771900-
dc.scopusid9239275100-
dc.affiliationChan, S.-C., Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University (NTU), 21 Nanyang Link, Singapore, 637371, Singapore-
dc.affiliationAng, Z.Z., Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University (NTU), 21 Nanyang Link, Singapore, 637371, Singapore-
dc.affiliationGupta, P., Max-Plank-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, Mülheim an der Ruhr, D-45470, Germany-
dc.affiliationGanguly, R., Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University (NTU), 21 Nanyang Link, Singapore, 637371, Singapore-
dc.affiliationLi, Y., Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University (NTU), 21 Nanyang Link, Singapore, 637371, Singapore-
dc.affiliationYe, S., Max-Plank-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, Mülheim an der Ruhr, D-45470, Germany, State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China-
dc.affiliationEngland, J., Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University (NTU), 21 Nanyang Link, Singapore, 637371, Singapore-
dc.description.fundingJ.E. thanks NTU for funding (Grant M4081442). P.G. and S.Y. gratefully acknowledge the financial support of the Max-Planck Society, in particular, the joint work space of MPI-CEC and MPI-KOFO. S.Y. is deeply indebted to Dr. Eckhard Bill for fruitful discussions. Nanyang Technological University, NTU: M4081442; Max-Planck-Gesellschaft, MPG-
dc.description.correspondingauthorYe, S.; Max-Plank-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, Germany; email: shengfa.ye@dicp.ac.cn-
Appears in Collections:Journal Publications [CY]

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