Advanced Search

Show simple item record

dc.contributor.authorYıldız, Cem B.
dc.contributor.authorŞası, Osman
dc.contributor.authorAzizoğlu, Akın
dc.date.accessioned2019-09-24T06:55:11Z
dc.date.available2019-09-24T06:55:11Z
dc.date.issued2017en_US
dc.identifier.issn0922-6168
dc.identifier.issn1568-5675
dc.identifier.urihttps://doi.org/10.1007/s11164-016-2836-9
dc.identifier.urihttps://hdl.handle.net/20.500.12462/6448
dc.descriptionŞası, Osman (Balikesir Author)en_US
dc.description.abstractDensity functional theory and ab initio computations elucidated the ring-opening of substituted (R = -CF3, -CN, -CH3, -H, -NH2, -OCH3, -OH, -SiH3) 1-bromo-1-lithiosilirane 1 and 2-bromo-2-lithiosilirane 2 to LiBr complexes of 2-silaallene and 1-silaallene, respectively. Formally, two competitive pathways can be considered. The ring-opening reaction can take place through a concerted manner via TS3. Alternatively, the reaction may proceed in a stepwise fashion with the intermediacy of a free silacyclopropylidene-LiBr complex 7. In both cases, the position of the substituents determines the kinetic of the reactions. The structures with an electron-donating group are generally unstable, whereas the silacyclopropylidenoids bearing electron-withdrawing substituents are particularly stable species. Here, we propose the ring-opening of 5a-h to corresponding LiBr complexes of 2-silaallenes can proceed in both concerted and stepwise mechanism except for -H, -CH3, and -SiH3. The obtained activation energies for the ring-openings of 5a-h to related 2-silaallenes are too high for a reaction at room temperature with up to 61.4 kcal/mol. In contrast, the activation energy barriers for the isomerization of 6a-h to the LiBr complexes of 1-silaallenes was determined to be relatively low at the B3LYP/6-31+G(d,p), M06/6-31+G(d,p), and MP2/6-31+G(d,p) levels. Moreover, we have also investigated the solvent effect on the unsubstituted models using both implicit and explicit solvation models. The energy barriers of the solvated models are found to be slightly higher than the results of gas phase calculations. Additionally, the ring-opening of dimer 6 (6-Dim) is also calculated for the ring-opening mechanism with the energy barrier of 3.7 kcal/mol at B3LYP/6-31+G(d,p) level of theory.en_US
dc.description.sponsorshipAksaray University coordinator ship of cientific research projects 2016-024 "en_US
dc.language.isoengen_US
dc.publisherSpringeren_US
dc.relation.isversionof10.1007/s11164-016-2836-9en_US
dc.rightsinfo:eu-repo/semantics/embargoedAccessen_US
dc.subjectSilaalleneen_US
dc.subjectSilylenoiden_US
dc.subjectSubstituent Effectsen_US
dc.subjectSolvent Effecten_US
dc.subjectReactive Intermediateen_US
dc.subjectReaction Mechanismen_US
dc.titleSolvent, substituent, and dimerization effects on the ring-opening mechanisms of monosilacyclopropylidenoids: a theoretical studyen_US
dc.typearticleen_US
dc.relation.journalResearch on Chemical Intermediatesen_US
dc.contributor.departmentFen Edebiyat Fakültesien_US
dc.contributor.authorID0000-0002-0424-4673en_US
dc.contributor.authorID0000-0002-5098-1842en_US
dc.identifier.volume43en_US
dc.identifier.issue7en_US
dc.identifier.startpage3711en_US
dc.identifier.endpage3726en_US
dc.relation.tubitakinfo:eu-repo/grantAgreement/TUBITAK/TBAG-212T049en_US
dc.relation.publicationcategoryMakale - Uluslararası Hakemli Dergi - Kurum Öğretim Elemanıen_US


Files in this item

Thumbnail

This item appears in the following Collection(s)

Show simple item record