A structural and spectroscopic study of tris-aryl substituted R 3PI 2 adducts

Nicholas A. Barnes, Stephen M. Godfrey, Rana Z. Khan, Amber Pierce, Robin G. Pritchard

    Research output: Contribution to journalArticlepeer-review

    Abstract

    A series of Ar 3PI 2 adducts [Ar = (o-OCH 3C 6H 4), (m-OCH 3C 6H 4), (p-OCH 3C 6H 4), (o-SCH 3C 6H 4), (p-SCH 3C 6H 4), (m-FC 6H 4), (p-FC 6H 4), (p-ClC 6H 4)] have been synthesized via the 1:1 reactions of Ar 3P with di-iodine. The 31P{ 1H} NMR spectra of a series of Ar 3PI 2 adducts has been examined to resolve previous inconsistent reports. Ar 3PI 2 adducts do not ionize to [Ar 3PI]I in CDCl 3, and in many cases the molecular Ar 3PI 2 "spoke" adduct is stable in solution, with the degree of stability being highly dependent on the nature of the aryl group. The structures of the majority of these adducts have been established by X-ray diffraction studies. Whilst P-I and I-I bond lengths are primarily influenced by electronic effects, steric and crystal packing effects may also have an influence, as shown by the different polymorphs of (p-FC 6H 4) 3PI 2, where a change in the conformation of the aryl groups in one of the molecules results in a lengthening of the P-I bond and shortening of the I-I bond. © 2012 Elsevier Ltd. All rights reserved.
    Original languageEnglish
    Pages (from-to)31-46
    Number of pages15
    JournalPolyhedron
    Volume35
    Issue number1
    DOIs
    Publication statusPublished - 16 Mar 2012

    Keywords

    • Charge transfer adducts
    • Crystal packing
    • Iodine
    • Ligand conformation
    • Phosphines

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