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Hydrogen/Halogen Exchange of Phosphines for the Rapid Formation of Cyclopolyphosphines.
Barrett, Adam N; Woof, Callum R; Goult, Christopher A; Gasperini, Danila; Mahon, Mary F; Webster, Ruth L.
Afiliación
  • Barrett AN; Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, United Kingdom.
  • Woof CR; Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, United Kingdom.
  • Goult CA; Department of Chemistry, University of York, Heslington, York YO10 5DD, United Kingdom.
  • Gasperini D; Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, United Kingdom.
  • Mahon MF; Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, United Kingdom.
  • Webster RL; Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, United Kingdom.
Inorg Chem ; 60(21): 16826-16833, 2021 Nov 01.
Article en En | MEDLINE | ID: mdl-34647448
The hydrogen/halogen exchange of phosphines has been exploited to establish a truly useable substrate scope and straightforward methodology for the formation of cyclopolyphosphines. Starting from a single dichlorophosphine, a sacrificial proton "donor phosphine" makes the rapid, mild synthesis of cyclopolyphosphines possible: reactions are complete within 10 min at room temperature. Novel (aryl)cyclopentaphosphines (ArP)5 have been formed in good conversion, with the crystal structures presented. The use of catalytic quantities of iron(III) acetylacetonate provides significant improvements in conversion in the context of diphosphine (Ar2P)2 and alkyl-substituted cyclotetra- or cyclopentaphosphine ((AlkylP)n, where n = 4 or 5) formation. Both iron-free and iron-mediated reactions show high levels of selectivity for one specific ring size. Finally, investigations into the reactivity of Fe(acac)3 suggest that the iron species is acting as a sink for the hydrochloric acid byproduct of the reaction.
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Inorg Chem Año: 2021 Tipo del documento: Article País de afiliación: Reino Unido Pais de publicación: Estados Unidos
Texto completo
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Inorg Chem Año: 2021 Tipo del documento: Article País de afiliación: Reino Unido Pais de publicación: Estados Unidos