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

Abstract

Three new uranium species (C₅Me₅)₂U(N-2,6-ⁱPr₂-C₆H₃)(S), (C₅Me₅)₂U(N-2,6-ⁱPr₂-C₆H₃)(η²-S₂), and (C₅Me₅)₂U(N-2,6-ⁱPr₂-C₆H₃)(SPMe₃) 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(N-2,6-ⁱPr₂-C₆H₃)(S) and (C₅Me₅)₂U(N-2,6-ⁱPr₂-C₆H₃)(η²-S₂) were also determined. The compound (C₅Me₅)₂U(N-2,6-ⁱPr₂-C₆H₃)(S) is the first neutral uranium complex with a terminal sulphido ligand, and (C₅Me₅)₂U(N-2,6-ⁱPr₂-C₆H₃)(SPMe₃) is the first uranium compound with a coordinated phosphine sulphide ligand. The phosphine sulphide adduct, (C₅Me₅)₂U(N-2,6-ⁱPr₂-C₆H₃)(SPMe₃), can be synthesized either by reaction of the uranium(IV) complex (C₅Me₅)₂U(N-2,6-ⁱPr₂-C₆H₃)(thf) with SPMe₃ or by the reaction of the uranium(VI) terminal sulphido complex (C₅Me₅)₂U(N-2,6-ⁱPr₂-C₆H₃)(S) with PMe₃.