Atomic uranium cations, U+ and U2+, reacted with the facile sulfur-atom donor OCS to produce several monopositive and dipositive uranium sulfide species containing up to four sulfur atoms. Sequential abstraction of two sulfur atoms by U2+ resulted in US22+; density functional theory computations indicate that the ground-state structure for this species is side-on eta(2)-S-2 triangular US22+, with the linear thiouranyl isomer, {S= U-VI=S}(2+), some 171 kJ mol(-1) higher in energy. The result that the linear thiouranyl structure is a local minimum at a moderate energy suggests that it should be feasible to stabilize this moiety in molecular compounds.