NDLI: An anionic phosphenium complex as an ambident nucleophile

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Nieger, M. Frey, W. Bender, J. Förster, D. Stadelmann, B. Gudat, D.
Description	Author Affiliation: Stadelmann B ( Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70550 Stuttgart, Germany. gudat@iac.uni-stuttgart.de.)
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, $ClSnPh_{3},$ 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 °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 π-acceptor behaviour but show no disposition to adopt phosphide-like character or formally oxidize the metal centre.
ISSN	14779226
Issue Number	13
Journal	Dalton Trans.
Volume Number	44
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2015-04-07
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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