UCL Discovery

Abstract

Products from the thermolysis of PhNCO and [MoO2(S2CNR2)(2)] (R = Me, Et) are highly dependent upon the reaction conditions. When carried out in air, the major products are cations, [Mo(NPh)(S2CNR2)(3)](+), as shown by a crystal structure of [Mo(NPh)(S2CNEt2)(3)](2)[Mo6O19]. Under rigorously anaerobic conditions, reaction of two equivalents of PhNCO with [MoO2(S2CNR2)(2)] affords [Mo(NPh)(2)(S2CNR2)(2)] as the major product. However, chloroform solutions of the bis(imido) complexes hydrolyze in air to afford [Mo(NPh)(S2CNR2)(2)(mu-MoO4)](2), in which molybdate groups bridge between molybdenum(VI) imido-bis(dithiocarbamate) centers. These results are placed in context of our earlier studies of these reactions that lead to the formation of oxo-disulfide [MoS2(NPh)(S2CNR2)(2)] and dimeric molybdenum(V) [MoO(mu-NPh)(S2CNR2)](2) complexes, thus allowing a full picture of these transformations to be established.Heating PhNCO with [MoO2(S2CNR2)(2)] in air gives [Mo(NPh)(S2CNR2)(3)]X (R = Me, Et), but when the reaction is carried out under anaerobic conditions, [Mo(NPh)(2)(S2CNR2)(2)] initially results, chloroform solutions of which hydrolyze in air to afford [Mo(NPh)(S2CNR2)(2)(mu-MoO4)](2).