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dc.contributor.authorTuononen, Heikki
dc.contributor.authorRoesler, Roland
dc.contributor.authorDutton, Jason
dc.contributor.authorRagogna, Paul
dc.date.accessioned2015-11-20T08:49:11Z
dc.date.available2015-11-20T08:49:11Z
dc.date.issued2007
dc.identifier.citationTuononen, H., Roesler, R., Dutton, J., & Ragogna, P. (2007). Electronic Structures of Main-Group Carbene Analogues. <i>Inorganic Chemistry</i>, <i>46</i>(25), 10693-10706. <a href="https://doi.org/10.1021/ic701350e" target="_blank">https://doi.org/10.1021/ic701350e</a>
dc.identifier.otherCONVID_17432706
dc.identifier.otherTUTKAID_28500
dc.identifier.urihttps://jyx.jyu.fi/handle/123456789/47764
dc.description.abstractThe electronic structures of 15 group 13−16 carbene analogues are analyzed using various quantum chemical methods and compared to the data obtained for the parent N-heterocyclic carbene (NHC), imidazol-2-ylidene. The results of this study present a uniform analysis of the similarities and differences in the electronic structures of p-block main-group carbene analogues. Though all systems are formally isovalent, the theoretical analyses unambiguously indicate that their electronic structures run the gamut from CC localized (group 13) to CN localized (group 16) via intermediate, more delocalized, systems. In particular, neither the stibenium ion nor any of the chalcogenium dications is a direct analogue of imidazol-2-ylidene as they all contain two lone pairs of electrons around the divalent main-group center, instead of the expected one. The reason behind the gradual change in the electronic structure of main-group analogues of imidazol-2-ylidene was traced to the total charge of the systems, which changes from anionic to dicationic when moving from left to right in the periodic table. Results from theoretical analyses of aromaticity show that all group 13−16 analogues of imidazol-2-ylidene display some degree of aromatic character. The heavier group 13 anions benefit the least from π-electron delocalization, whereas the cationic group 15 systems are on par with the parent carbon system and display only slightly less aromatic character than cyclopentadienide, a true 6π-electron aromatic species. The σ-donor and π-acceptor ability of the different main-group carbene analogues are also evaluated.
dc.language.isoeng
dc.publisherACS
dc.relation.ispartofseriesInorganic Chemistry
dc.subject.otherN-heterosykliset karbeenit
dc.subject.otherelektronirakenne
dc.subject.otherN-heterocyclic carbenes
dc.subject.otherelectronic structure
dc.titleElectronic Structures of Main-Group Carbene Analogues
dc.typearticle
dc.identifier.urnURN:NBN:fi:jyu-201511183709
dc.contributor.laitosKemian laitosfi
dc.contributor.laitosDepartment of Chemistryen
dc.contributor.oppiaineEpäorgaaninen ja analyyttinen kemiafi
dc.contributor.oppiaineInorganic and Analytical Chemistryen
dc.type.urihttp://purl.org/eprint/type/JournalArticle
dc.date.updated2015-11-18T13:15:24Z
dc.type.coarhttp://purl.org/coar/resource_type/c_2df8fbb1
dc.description.reviewstatuspeerReviewed
dc.format.pagerange10693-10706
dc.relation.issn0020-1669
dc.relation.numberinseries25
dc.relation.volume46
dc.type.versionacceptedVersion
dc.rights.copyright© 2007 American Chemical Society. This is a final draft version of an article whose final and definitive form has been published by ACS. Published in this repository with the kind permission of the publisher.
dc.rights.accesslevelopenAccessfi
dc.relation.doi10.1021/ic701350e
dc.type.okmA1


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