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Thorium–phosphorus triamidoamine complexes containing Th–P single- and multiple-bond interactions

Author

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  • Elizabeth P. Wildman

    (School of Chemistry, The University of Manchester)

  • Gábor Balázs

    (Institute of Inorganic Chemistry, University of Regensburg)

  • Ashley J. Wooles

    (School of Chemistry, The University of Manchester)

  • Manfred Scheer

    (Institute of Inorganic Chemistry, University of Regensburg)

  • Stephen T. Liddle

    (School of Chemistry, The University of Manchester)

Abstract

Despite the burgeoning field of uranium-ligand multiple bonds, analogous complexes involving other actinides remain scarce. For thorium, under ambient conditions only a few multiple bonds to carbon, nitrogen, oxygen, sulfur, selenium and tellurium are reported, and no multiple bonds to phosphorus are known, reflecting a general paucity of synthetic methodologies and also problems associated with stabilising these linkages at the large thorium ion. Here we report structurally authenticated examples of a parent thorium(IV)–phosphanide (Th–PH2), a terminal thorium(IV)–phosphinidene (Th=PH), a parent dithorium(IV)–phosphinidiide (Th–P(H)-Th) and a discrete actinide–phosphido complex under ambient conditions (Th=P=Th). Although thorium is traditionally considered to have dominant 6d-orbital contributions to its bonding, contrasting to majority 5f-orbital character for uranium, computational analyses suggests that the bonding of thorium can be more nuanced, in terms of 5f- versus 6d-orbital composition and also significant involvement of the 7s-orbital and how this affects the balance of 5f- versus 6d-orbital bonding character.

Suggested Citation

  • Elizabeth P. Wildman & Gábor Balázs & Ashley J. Wooles & Manfred Scheer & Stephen T. Liddle, 2016. "Thorium–phosphorus triamidoamine complexes containing Th–P single- and multiple-bond interactions," Nature Communications, Nature, vol. 7(1), pages 1-11, November.
  • Handle: RePEc:nat:natcom:v:7:y:2016:i:1:d:10.1038_ncomms12884
    DOI: 10.1038/ncomms12884
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