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Preparation of an ion with the highest calculated proton affinity: ortho-diethynylbenzene dianion

Poad, Berwyck L.J.; Reed, Nicholas D.; Hansen, Christopher S.; Trevitt, Adam J.; Blanksby, Stephen James; Mackay, Emily; Sherburn, Michael; Chan, Bun; Radom, Leo

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Owing to the increased proton affinity that results from additional negative charges, multiply-charged anions have been proposed as one route to prepare and access a range of new and powerful "superbases". Paradoxically, while the additional electrons in polyanions increase basicity they serve to diminish the electron binding energy and thus, it had been thought, hinder experimental synthesis. We report the synthesis and isolation of the ortho-diethynylbenzene dianion (ortho-DEB2-) and present...[Show more]

dc.contributor.authorPoad, Berwyck L.J.
dc.contributor.authorReed, Nicholas D.
dc.contributor.authorHansen, Christopher S.
dc.contributor.authorTrevitt, Adam J.
dc.contributor.authorBlanksby, Stephen James
dc.contributor.authorMackay, Emily
dc.contributor.authorSherburn, Michael
dc.contributor.authorChan, Bun
dc.contributor.authorRadom, Leo
dc.date.accessioned2018-11-29T22:56:33Z
dc.date.available2018-11-29T22:56:33Z
dc.identifier.issn2041-6520
dc.identifier.urihttp://hdl.handle.net/1885/153558
dc.description.abstractOwing to the increased proton affinity that results from additional negative charges, multiply-charged anions have been proposed as one route to prepare and access a range of new and powerful "superbases". Paradoxically, while the additional electrons in polyanions increase basicity they serve to diminish the electron binding energy and thus, it had been thought, hinder experimental synthesis. We report the synthesis and isolation of the ortho-diethynylbenzene dianion (ortho-DEB2-) and present observations of this novel species undergoing gas-phase proton-abstraction reactions. Using a theoretical model based on Marcus-Hush theory, we attribute the stability of ortho-DEB2- to the presence of a barrier that prevents spontaneous electron detachment. The proton affinity of 1843 kJ mol-1 calculated for this dianion superbase using high-level quantum chemistry calculations significantly exceeds that of the lithium monoxide anion, the most basic system previously prepared. The ortho-diethynylbenzene dianion is therefore the strongest base that has been experimentally observed to date.
dc.format.mimetypeapplication/pdf
dc.publisherRoyal Society of Chemistry
dc.sourceChemical Science
dc.titlePreparation of an ion with the highest calculated proton affinity: ortho-diethynylbenzene dianion
dc.typeJournal article
local.description.notesImported from ARIES
local.identifier.citationvolume7
dc.date.issued2016
local.identifier.absfor030500 - ORGANIC CHEMISTRY
local.identifier.absfor030502 - Natural Products Chemistry
local.identifier.absfor030700 - THEORETICAL AND COMPUTATIONAL CHEMISTRY
local.identifier.ariespublicationa383154xPUB4260
local.type.statusPublished Version
local.contributor.affiliationPoad, Berwyck L.J., Queensland University of Technology
local.contributor.affiliationReed, Nicholas D., University of Wollongong
local.contributor.affiliationHansen, Christopher S., University of Wollongong
local.contributor.affiliationTrevitt, Adam J., University of Wollongong
local.contributor.affiliationBlanksby, Stephen James, University of Wollongong
local.contributor.affiliationMackay, Emily, College of Science, ANU
local.contributor.affiliationSherburn, Michael, College of Science, ANU
local.contributor.affiliationChan, Bun, University of Sydney
local.contributor.affiliationRadom, Leo, University of Sydney
local.bibliographicCitation.issue9
local.bibliographicCitation.startpage6245
local.bibliographicCitation.lastpage6250
local.identifier.doi10.1039/c6sc01726f
dc.date.updated2018-11-29T08:12:57Z
local.identifier.scopusID2-s2.0-84983456976
local.identifier.thomsonID000382488500077
dcterms.accessRightsOpen Access
CollectionsANU Research Publications

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