Ring-opening mechanism of disilacyclopropylidenoids and trisilacyclopropylidenoid: A theoretical study

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dc.contributor.authorAzizoğlu, Akın
dc.contributor.authorYıldız, Cem Burak
dc.date.accessioned13.07.201910:50:10
dc.date.accessioned2019-07-16T08:23:17Z
dc.date.available13.07.201910:50:10
dc.date.available2019-07-16T08:23:17Z
dc.date.issued2012
dc.departmentAksaray Teknik Bilimler Meslek Yüksekokulu
dc.description.abstractAb-initio and density functional theory calculations have been performed to investigate the ring-opening reactions of 1-bromo-1-lithiodisilirane (5), 3-bromo-3-lithiodisilirane (6), and 1-bromo-1-lithiotrisilirane (7) to 1,2-disilaallene (9), 1,3-disilaallene (10), and trisilaallene (11), respectively. Formally, the ring-opening mechanism of silacyclopropylidenoids may be either concerted or stepwise involving the intermediacy of a free silacyclopropylidene or cyclopropylidene. The ring-opening of 5 to 9 can proceed in both concerted and stepwise mechanism, where high activation energy barriers need to be overcome in order to open the silacyclopropylidene ring and to generate 9. In contrast, the ring-opening reactions of 6 and 7 can occur in a concerted fashion. The activation energy barrier for the isomerization of 6 to the complex of 10 with LiBr was determined to be only 2.3 kcal/mol at the B3LYP/6-31G(d) level, and the reaction is highly exothermic, by 37.0 kcal/mol, which makes this reaction for a promising strategy for the synthesis of 1,3-disilaallenes. However, the barrier for the conversion of 7 to 11 is calculated to be quite high, 27.5 kcal/mol, and in this case the reaction is endothermic, by 8.8 kcal/mol. © 2012 Elsevier B.V. All rights reserved.
dc.description.sponsorshipThis work was supported by grants from the Scientific and Technical Research Council of Turkey (TUBITAK) ( Grant No . TUBITAK TBAG-210T113 ). Appendix A
dc.identifier.doi10.1016/j.jorganchem.2012.05.007
dc.identifier.endpage25en_US
dc.identifier.issn0022-328X
dc.identifier.scopusqualityQ2
dc.identifier.startpage19en_US
dc.identifier.urihttps://dx.doi.org/10.1016/j.jorganchem.2012.05.007
dc.identifier.urihttps://hdl.handle.net/20.500.12451/2737
dc.identifier.volume715en_US
dc.identifier.wosqualityN/A
dc.indekslendigikaynakWeb of Science
dc.indekslendigikaynakScopus
dc.language.isoen
dc.publisherElsevier
dc.relation.ispartofJournal of Organometallic Chemistry
dc.relation.publicationcategoryMakale - Uluslararası Hakemli Dergi - Kurum Öğretim Elemanı
dc.rightsinfo:eu-repo/semantics/openAccess
dc.subjectMP2
dc.subjectReaction Mechanism
dc.subjectSilaallene
dc.subjectSilacyclopropylidene
dc.subjectTheoretical Calculation
dc.titleRing-opening mechanism of disilacyclopropylidenoids and trisilacyclopropylidenoid: A theoretical study
dc.typeArticle

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