Diverse reactivity of an electrophilic phosphasilene towards anionic nucleophiles: Substitution or metal-amino exchange

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dc.authoridScheschkewitz, David -- 0000-0001-5600-8034; Yildiz, Cem Burak -- 0000-0002-0424-4673
dc.contributor.authorWillmes, Philipp
dc.contributor.authorJunk, Lukas
dc.contributor.authorHuch, Volker
dc.contributor.authorYıldız, Cem Burak
dc.contributor.authorScheschkewitz, David
dc.date.accessioned13.07.201910:50:10
dc.date.accessioned2019-07-29T19:28:49Z
dc.date.available13.07.201910:50:10
dc.date.available2019-07-29T19:28:49Z
dc.date.issued2016
dc.departmentTeknik Bilimler Meslek Yüksekokulu
dc.description.abstractThe reaction of MesLi (Mes=2,4,6-trimethylphenyl) with the electrophilic phosphasilene R-2(NMe2)Si-RSi=PNMe2 (2, R=Tip=2,4,6-triisopropylphenyl) cleanly affords R-2(NMe2)Si-RSi=PMes and thus provides the first example of a substitution reaction at an unperturbed Si=P bond. In toluene, the reaction of 2 with lithium disilenide, R2Si=Si(R)Li (1), apparently proceeds via an initial nucleophilic substitution step as well (as suggested by DFT calculations), but affords a saturated bicyclo[1.1.0]butane analogue as the final product, which was further characterized as its Fe(CO)(4) complex. In contrast, in 1,2-dimethoxyethane the reaction of 1 with 2 results in an unprecedented metal-amino exchange reaction.
dc.description.sponsorshipDeutsche Forschungsgemeinschaft (DFG) [SCHE906/4-1]; Alfried Krupp von Bohlen und Halbach-Foundation; COST Action [CM1302]
dc.description.sponsorshipFunding by the Deutsche Forschungsgemeinschaft (DFG SCHE906/4-1), the Alfried Krupp von Bohlen und Halbach-Foundation, and COST Action CM1302 (Smart Inorganic Polymers) is gratefully acknowledged. We thank the reviewers for their helpful comments.
dc.identifier.doi10.1002/anie.201605699
dc.identifier.endpage10917en_US
dc.identifier.issn1433-7851
dc.identifier.issn1521-3773
dc.identifier.issue36en_US
dc.identifier.pmid27509901
dc.identifier.scopusqualityQ1
dc.identifier.startpage10913en_US
dc.identifier.urihttps://doi.org/10.1002/anie.201605699
dc.identifier.urihttps://hdl.handle.net/20.500.12451/6090
dc.identifier.volume55en_US
dc.identifier.wosWOS:000383473600074
dc.identifier.wosqualityN/A
dc.indekslendigikaynakWeb of Science
dc.indekslendigikaynakScopus
dc.indekslendigikaynakPubMed
dc.language.isoen
dc.publisherWILEY-V C H Verlag Gmbh
dc.relation.ispartofAngewandte Chemie-International Edition
dc.relation.publicationcategoryMakale - Uluslararası Hakemli Dergi - Kurum Öğretim Elemanı
dc.rightsinfo:eu-repo/semantics/openAccess
dc.subjectBicyclic Compounds
dc.subjectElectrophiles
dc.subjectPhosphasilenes
dc.subjectPhosphorus
dc.subjectSilicon
dc.titleDiverse reactivity of an electrophilic phosphasilene towards anionic nucleophiles: Substitution or metal-amino exchange
dc.typeArticle

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