Andrew Behrle - Systematic Investigation of Thorium(IV)– and Uranium(IV)–Ligand Bonding in Dithiophosphonate, Thioselenophosphinate, and Diselenophosphonate Complexes

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  Publication Details (including relevant citation   information):

    Department of Chemistry, University of Missouri−Columbia, 601 S.     College Avenue, Columbia, Missouri 65211-7600, United States 
    Department of Chemistry, Christopher Ingold     Laboratories, University College     London, 20 Gordon Street, London WC1H 0AJ, United Kingdom 
  Inorg. Chem., 2013, 52 (18), pp 10623–10631
  DOI: 10.1021/ic401642a


  Homoleptic soft-donor actinide complexes of the general form   An[E2PROR′]4 were synthesized from salt   metathesis between ThCl4(DME)2 or   UI4(1,4-dioxane)2 and   M[E2PROR′], M = Na, K, to yield 2 (An   = Th, E = S, R = 4-MeOC6H4, R′ = Me),   3 (An = Th, E = S, R =   4-MeOC6H4, R′ = tBu),   4 (An = U, E = S, R =   4-MeOC6H4, R′ = Me), 5 (An   = Th, E = Se, R = C6H5, R′ = Me), and   6 (An = U, E = Se, R =   C6H5, R′ = Me). In addition thorium and   uranium thioselenophosphinate complexes 7 and   8 were produced from the reaction of   ThCl4(DME)2 and   UI4(1,4-dioxane)2 and   Na[SSePPh2], respectively. All compounds were   characterized using elemental analysis, 1H and   31P NMR, and IR spectroscopy, and the U(IV) compounds   were also examined with UV–vis spectroscopy. The 77Se   NMR spectrum of 5 reveals the first reported   resonance with a Th–Se bond. The solid-state structures of   2, 5, 7, and   8 were determined by X-ray crystallography. The   actinide–ligand bonding was examined using density functional   theory calculations in conjunction with quantum theory of   atoms-in-molecules analysis and shows slightly increased   covalency in actinide–selenium bonds than actinide–sulfur.

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