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dc.contributor.authorConradie, Jeanet
dc.contributor.authorBrothers, Penelope Jane
dc.contributor.authorGhosh, Abhik
dc.date.accessioned2020-04-28T07:11:30Z
dc.date.available2020-04-28T07:11:30Z
dc.date.issued2019-03-15
dc.description.abstractA careful density functional theory reexamination of the geometric and electronic structures of reduced main-group porphyrin complexes E(Por)L2 (E = Si or Ge; L = pyridine or tetrahydrofuran), B2(Por), and C2(Por) has confirmed these as pure isophlorin derivatives with normal-valent coordinated central atoms. Only axially unligated Ge(Por) and the dications [B2(Por)]2+ and [C2(Por)]2+ feature aromatic porphyrin ligands. The calculations faithfully reproduce the strong bond-length alternation along the outer rim of the macrocycle in the reduced complexes, consistent with antiaromatic character, as well as much stronger ruffling in the reduced group 14 complexes relative to their nonreduced counterparts such as E(Por)X2 (E = Si or Ge; X = F or Cl). The latter is thought to reflect the lower barrier to nonplanar deformation for the antiaromatic systems. In addition, unlike B2(Por) and its dication, which are planar, C2(Por) and its dication are predicted to be strongly ruffled, reflecting the smaller size of the central C2 unit. The calculations also predict characteristically low ionization potentials and singlet–triplet gaps for the antiaromatic complexes. A brief exploratory study of the as-yet-unknown group 15 complexes E(TPP)(Ph)(py), where E = P and As, also indicated an antiaromatic isophlorin macrocycle coordinated to a pentavalent group 15 center.en_US
dc.descriptionPublisher's statement (option C): <a href=https://pubs.acs.org/page/4authors/authorchoice/options.html>https://pubs.acs.org/page/4authors/authorchoice/options.html</a>en_US
dc.identifier.citationConradie, J; Brothers, PJ; Ghosh, A. (2019) Main-Group-Element Isophlorin Complexes Revisited: The Question of a Subvalent Central Atom.<i> Inorganic Chemistry, 58,</i> (7), 4634-4640.en_US
dc.identifier.cristinIDFRIDAID 1703250
dc.identifier.doi10.1021/acs.inorgchem.9b00201
dc.identifier.issn0020-1669
dc.identifier.issn1520-510X
dc.identifier.urihttps://hdl.handle.net/10037/18140
dc.language.isoengen_US
dc.publisherACS Publicationsen_US
dc.relation.journalInorganic Chemistry
dc.relation.projectIDNorges forskningsråd: 262229en_US
dc.rights.accessRightsopenAccessen_US
dc.rights.holderCopyright © 2019 American Chemical Societyen_US
dc.subjectVDP::Mathematics and natural science: 400::Chemistry: 440en_US
dc.subjectVDP::Matematikk og Naturvitenskap: 400::Kjemi: 440en_US
dc.titleMain-Group-Element Isophlorin Complexes Revisited: The Question of a Subvalent Central Atomen_US
dc.type.versionacceptedVersionen_US
dc.typeJournal articleen_US
dc.typeTidsskriftartikkelen_US
dc.typePeer revieweden_US


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