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A sulphur and uranium fiesta! Synthesis, structure, and characterization of neutral terminal uranium(VI) monosulphide, uranium(VI) η2-disulphide, and uranium(IV) phosphine sulphide complexes

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Abstract

Three new uranium species (C5Me5)2U([double bond, length as m-dash]N-2,6-iPr2-C6H3)([double bond, length as m-dash]S), (C5Me5)2U([double bond, length as m-dash]N-2,6-iPr2-C6H3)(η2-S2), and (C5Me5)2U([double bond, length as m-dash]N-2,6-iPr2-C6H3)(S[double bond, length as m-dash]PMe3) were synthesized and fully characterized by a combination of NMR, IR, and UV/vis–NIR spectroscopies, elemental analysis, and cyclic voltammetry. The solid state structures of (C5Me5)2U([double bond, length as m-dash]N-2,6-iPr2-C6H3)([double bond, length as m-dash]S) and (C5Me5)2U([double bond, length as m-dash]N-2,6-iPr2-C6H3)(η2-S2) were also determined. The compound (C5Me5)2U([double bond, length as m-dash]N-2,6-iPr2-C6H3)([double bond, length as m-dash]S) is the first neutral uranium complex with a terminal sulphido ligand, and (C5Me5)2U([double bond, length as m-dash]N-2,6-iPr2-C6H3)(S[double bond, length as m-dash]PMe3) is the first uranium compound with a coordinated phosphine sulphide ligand. The phosphine sulphide adduct, (C5Me5)2U([double bond, length as m-dash]N-2,6-iPr2-C6H3)(S[double bond, length as m-dash]PMe3), can be synthesized either by reaction of the uranium(IV) complex (C5Me5)2U([double bond, length as m-dash]N-2,6-iPr2-C6H3)(thf) with S[double bond, length as m-dash]PMe3 or by the reaction of the uranium(VI) terminal sulphido complex (C5Me5)2U([double bond, length as m-dash]N-2,6-iPr2-C6H3)([double bond, length as m-dash]S) with PMe3.

Graphical abstract: A sulphur and uranium fiesta! Synthesis, structure, and characterization of neutral terminal uranium(vi) monosulphide, uranium(vi) η2-disulphide, and uranium(iv) phosphine sulphide complexes

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Publication details

The article was received on 18 Jul 2018, accepted on 25 Sep 2018 and first published on 26 Sep 2018


Article type: Paper
DOI: 10.1039/C8DT02932F
Citation: Dalton Trans., 2019, Advance Article
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    A sulphur and uranium fiesta! Synthesis, structure, and characterization of neutral terminal uranium(VI) monosulphide, uranium(VI) η2-disulphide, and uranium(IV) phosphine sulphide complexes

    J. K. Pagano, D. S. J. Arney, B. L. Scott, D. E. Morris, J. L. Kiplinger and C. J. Burns, Dalton Trans., 2019, Advance Article , DOI: 10.1039/C8DT02932F

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