A sulphur and uranium fiesta! Synthesis, structure, and characterization of neutral terminal uranium(VI) monosulphide, uranium(VI) η 2 -disulphide, and uranium(IV) phosphine sulphide complexes
Here, three new uranium species (C 5 Me 5 ) 2 U(=N-2,6- i Pr 2 -C 6 H 3 )(=S), (C 5 Me 5 ) 2 U(=N-2,6- i Pr 2 -C 6 H 3 )(η 2 -S 2 ), and (C 5 Me 5 ) 2 U(=N-2,6- i Pr 2 -C 6 H 3 )(S=PMe 3 ) 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 (C 5 Me 5 ) 2 U(=N-2,6- i Pr 2 -C 6 H 3 )(=S) and (C 5 Me 5 ) 2 U(=N-2,6- i Pr 2 -C 6 H 3 )(η 2 -S 2 ) were also determined. The compound (C 5 Me 5 ) 2 U(=N-2,6- i Pr 2 -C 6 H 3 )(=S) is the first neutral uranium complex with a terminal sulphido ligand, and (C 5 Me 5 ) 2 U(=N-2,6- i Pr 2 -C 6 H 3 )(S=PMe 3 ) is the first uranium compound with a coordinated phosphine sulphide ligand. The phosphine sulphide adduct, (C 5 Me 5 ) 2 U(=N-2,6- i Pr 2 -C 6 H 3 )(S=PMe 3 ), can be synthesized either by reaction of the uranium(IV) complex (C 5 Me 5 ) 2 U(=N-2,6- i Pr 2 -C 6 H 3 )(thf) with S=PMe 3 or by the reaction of the uranium(VI) terminal sulphido complex (C 5 Me 5 ) 2 U(=N-2,6- i Pr 2 -C 6 H 3 )(=S) with PMe 3 .