title: Synthesis and properties of uranium sulfide cations. An evaluation of the stability of thiouranyl, {S═U═S}2+.
abstract: Atomic uranium cations, U(+) and U(2+), 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 U(2+) resulted in US2(2+); density functional theory computations indicate that the ground-state structure for this species is side-on η(2)-S2 triangular US2(2+), 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.
authors.affiliation: Centro de Ciências e Tecnologias Nucleares, Instituto Superior Técnico, Universidade de Lisboa , 2695-066 Bobadela LRS, Portugal.
authors.forename: Cláudia C L
authors.initials: CC
authors.lastname: Pereira
authors.forename: Maria del Carmen
authors.initials: Mdel C
authors.lastname: Michelini
authors.forename: Joaquim
authors.initials: J
authors.lastname: Marçalo
authors.forename: Yu
authors.initials: Y
authors.lastname: Gong
authors.forename: John K
authors.initials: JK
authors.lastname: Gibson