An anionic phosphenium complex as an ambident nucleophile

Show simple item record Stadelmann, B. Bender, J. Förster, D. Frey, W. Nieger, M. Gudat, D. 2017-10-02T07:45:01Z 2017-10-02T07:45:01Z 2015
dc.identifier.citation Stadelmann , B , Bender , J , Förster , D , Frey , W , Nieger , M & Gudat , D 2015 , ' An anionic phosphenium complex as an ambident nucleophile ' , Dalton Transactions , vol. 44 , no. 13 , pp. 6023-6031 .
dc.identifier.other PURE: 48130933
dc.identifier.other PURE UUID: b004fdc2-34f8-44e5-84f7-d900ed289af1
dc.identifier.other WOS: 000351476600013
dc.identifier.other Scopus: 84925340594
dc.identifier.other ORCID: /0000-0003-1677-0109/work/28845875
dc.description.abstract A unique anionic phosphenium complex was prepared from reaction of an N-heterocyclic chlorophosphine with Collman's reagent or K[HFe(CO)(4)]/NaH and characterized by spectral and XRD data. The complex behaves as an ambident nucleophile. Reactions with acetic acid, ClSnPh3, and a further equivalent of an N-heterocyclic chlorophosphine proceed via electrophilic functionalization at the metal site to yield appropriate mono- or bis-phosphenium complexes. Reaction with MeI at -70 degrees C produces a P-alkylation product as the first spectroscopically detectable intermediate, which decays at a higher temperature to give a mixture of free P-methylated N-heterocyclic phosphine and its Fe(CO)(4) complex. The different reaction products were characterized by spectral and XRD data. Computational studies indicate that the NHP units in all complexes display p-acceptor behaviour but show no disposition to adopt phosphide-like character or formally oxidize the metal centre. en
dc.format.extent 9
dc.language.iso eng
dc.relation.ispartof Dalton Transactions
dc.rights cc_by
dc.rights.uri info:eu-repo/semantics/openAccess
dc.subject SOLID-STATE
dc.subject ION COMPLEX
dc.subject REACTIVITY
dc.subject LIGANDS
dc.subject REAGENTS
dc.subject CATIONS
dc.subject 116 Chemical sciences
dc.title An anionic phosphenium complex as an ambident nucleophile en
dc.type Article
dc.contributor.organization Department of Chemistry
dc.contributor.organization Department
dc.description.reviewstatus Peer reviewed
dc.relation.issn 1477-9226
dc.rights.accesslevel openAccess
dc.type.version publishedVersion

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