Molybdenum(VI) imido complexes: formation of [Mo(NPh)(S2CNR2)3]X and [Mo(NPh)(S2CNR2)2(μ-MoO4)]2 (R = Me, Et) from the reaction of [MoO2(S2CNR2)2] and PhNCO under aerobic conditions
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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(μ-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(μ-NPh)(S2CNR2)]2 complexes, thus allowing a full picture of these transformations to be established.