An anionic phosphenium complex as an ambident nucleophile

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http://hdl.handle.net/10138/224663

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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 . https://doi.org/10.1039/c5dt00008d

Title: An anionic phosphenium complex as an ambident nucleophile
Author: Stadelmann, B.; Bender, J.; Förster, D.; Frey, W.; Nieger, M.; Gudat, D.
Other contributor: University of Helsinki, Department of Chemistry

Date: 2015
Language: eng
Number of pages: 9
Belongs to series: Dalton Transactions
ISSN: 1477-9226
DOI: https://doi.org/10.1039/c5dt00008d
URI: http://hdl.handle.net/10138/224663
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.
Subject: N-HETEROCYCLIC PHOSPHENIUM
TRANSITION-METAL-COMPLEXES
CRYSTAL-STRUCTURE
CARBONYL ANIONS
SOLID-STATE
ION COMPLEX
REACTIVITY
LIGANDS
REAGENTS
CATIONS
116 Chemical sciences
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