Hydrogen-Halogen Exchange of Phosphines for the Rapid Formation of Cyclopolyphosphines

Adam Barrett, Callum Woof, Christopher Goult, Danila Gasperini, Mary Mahon, Ruth Webster

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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.
Original languageEnglish
Pages (from-to)16826 - 16833
JournalInorganic Chemistry
Issue number21
Early online date14 Oct 2021
Publication statusPublished - 1 Nov 2021


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