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dc.contributor.authorTarai, Arup
dc.contributor.authorMallick, Jyotiprakash
dc.contributor.authorConradie, Jeanet
dc.contributor.authorKar, Sanjib
dc.contributor.authorGhosh, Abhik
dc.date.accessioned2024-01-05T12:43:05Z
dc.date.available2024-01-05T12:43:05Z
dc.date.issued2023-08-30
dc.description.abstractFree-base corroles have long been known to be acidic, readily undergoing deprotonation by mild bases and in polar solvents. The conjugate base, however, has not been structurally characterized until now. Presented here is a first crystal structure of a freebase corrole anion, derived from tris(p-cyanophenyl)corrole, as the tetrabuylammonium salt. The low-temperature (100 K) structure reveals localized hydrogens on a pair of opposite pyrrole nitrogens. DFT calculations identify such a structure as the global minimum but also point to two cis tautomers only 4−7 kcal/mol above the ground state. In terms of free energy, however, the cis tautomers are above or essentially flush with the trans-to-cis barrier so the cis tautomers are unlikely to exist or be observed as true intermediates. Thus, the hydrogen bond within each dipyrrin unit on either side of the molecular pseudo-C<sub>2</sub> axis through C<sub>10</sub> (i.e., between pyrrole rings A and B or between C and D) qualifies as or closely approaches a low-barrier hydrogen bond. Proton migration across the pseudo-C<sub>2</sub> axis entails much higher activation energies >20 kcal/mol, reflecting the relative rigidity of the molecule along the C<sub>1</sub>-C<sub>19</sub> pyrrole-pyrrole linkage.en_US
dc.identifier.citationTarai, Mallick, Singh, Conradie, Kar, Ghosh. Free-Base Corrole Anion. Journal of Organic Chemistry. 2023en_US
dc.identifier.cristinIDFRIDAID 2189259
dc.identifier.doi10.1021/acs.joc.3c01125
dc.identifier.issn0022-3263
dc.identifier.issn1520-6904
dc.identifier.urihttps://hdl.handle.net/10037/32353
dc.language.isoengen_US
dc.publisherAmerican Chemical Societyen_US
dc.relation.journalJournal of Organic Chemistry
dc.rights.accessRightsopenAccessen_US
dc.rights.holderCopyright 2023 The Author(s)en_US
dc.rights.urihttps://creativecommons.org/licenses/by/4.0en_US
dc.rightsAttribution 4.0 International (CC BY 4.0)en_US
dc.titleFree-Base Corrole Anionen_US
dc.type.versionpublishedVersionen_US
dc.typeJournal articleen_US
dc.typeTidsskriftartikkelen_US
dc.typePeer revieweden_US


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Attribution 4.0 International (CC BY 4.0)
Except where otherwise noted, this item's license is described as Attribution 4.0 International (CC BY 4.0)