Substituent effects on the ring-opening mechanism of gem-dibromospiropentanes to related allenes: A theoretical study

Basit Öğe Kaydı
dc.contributor.authorYıldız, Cem Burak
dc.contributor.authorAzizoğlu, Akın
dc.date.accessioned13.07.201910:50:10
dc.date.accessioned2019-07-16T08:21:52Z
dc.date.available13.07.201910:50:10
dc.date.available2019-07-16T08:21:52Z
dc.date.issued2016
dc.departmentAksaray Teknik Bilimler Meslek Yüksekokulu
dc.description.abstractDensity functional theory computations at B3LYP and X3LYP levels were performed for ring openings of substituted gem-dibromospiropentanes (R = -H, -Cl, -Br, -CH3, -SiH3, -OH, -OCH3, -CF3, -BF2, and -SH) to related allenes. The conversion of spiropentanoids 5a, 5b, 5c, 5d, 5e, 5f, 5g, 5h, 5i, 5j to the corresponding allenes 7a, 7b, 7c, 7d, 7e, 7f, 7g, 7h, 7i, 7j can proceed in both concerted and stepwise mechanism except for R = -H. Both ring-opening mechanisms have similar activation energy barriers to open the spiropentanylidene ring and generate the structure of allene at all theoretical levels used herein. Generally the ? electron-donating group (-OH or -SH) decreases the activation barrier for the follow-up reaction of 1-bromo-1-lithiospiropentanoid and free spiropentanylidene. Hence, both bearing electron-donating substituents are more reactive than those with electron-withdrawing group, and the first one to open the ring to the LiBr-allene complex does so more readily than the second. The sEDA index used to measure sigma-electron excess/deficiency of the cyclopropylidene ring is mutually correlated for the studied systems. Copyright © 2015 John Wiley & Sons, Ltd.
dc.identifier.doi10.1002/poc.3487
dc.identifier.endpage68en_US
dc.identifier.issn0894-3230
dc.identifier.issue2en_US
dc.identifier.scopusqualityQ3
dc.identifier.startpage63en_US
dc.identifier.urihttps://dx.doi.org/10.1002/poc.3487
dc.identifier.urihttps://hdl.handle.net/20.500.12451/2381
dc.identifier.volume29en_US
dc.identifier.wosqualityN/A
dc.indekslendigikaynakWeb of Science
dc.indekslendigikaynakScopus
dc.language.isoen
dc.publisherJohn Wiley and Sons Limited
dc.relation.ispartofJournal of Physical Organic Chemistry
dc.relation.publicationcategoryMakale - Uluslararası Hakemli Dergi - Kurum Öğretim Elemanı
dc.rightsinfo:eu-repo/semantics/closedAccess
dc.subjectCyclopropylidenoids
dc.subjectDFT
dc.subjectDoering-Moore-Skattebøl
dc.subjectGem-Dihalogenospiropentanes
dc.subjectSubstituent Effects
dc.titleSubstituent effects on the ring-opening mechanism of gem-dibromospiropentanes to related allenes: A theoretical study
dc.typeArticle

Dosyalar

Orijinal paket
Listeleniyor 1 - 1 / 1
[ X ]
İsim:
yildiz-cem burak-2015.pdf
Boyut:
1.32 MB
Biçim:
Adobe Portable Document Format
Açıklama:
Tam Metin / Full Text
İndir

Koleksiyon

Makale Koleksiyonu
Scopus İndeksli Yayınlar Koleksiyonu
WoS İndeksli Yayınlar Koleksiyonu