Syntheses and x-ray crystal structures of [MoO(SCH2CH2-CH2S)2]? and [Mo2O2(?-N3)(SCH2CH2CH2S)3]?. A study of the redox behaviour of [MoO(SCH2CH2S)2]? by cyclic voltammetry using convolution analysis

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The complexes [PPh4][MoO{S(CH2)nS}2], n=2 (1) n=3 (3), were synthesised from the MoVI dioxoprecursor complex [MoO2(butane-2,3-diolato)2] and the appropriate thiol in the presence of base. Complex (3) exhibits a square pyramidal geometry. Crystal Data: P21,0, Z=4,a=9.612(2),b=21.202(4),c=15.462(3) A, β=103.06(1)°, V=3043.3A3, F(000)=1364.0, 3687 reflections collected, and 1957 used in solution with R=0.058. [MoO(SCH2CH2CH2S)2]− reacts with hydrazoic acid in methanol to produce [Mo2O2(μ-N3)-(SCH2CH2CH2S)3] (5), crystal data:\(P_{2_{1} 2_{1} 2_{1} } \)a=9.398(3),b=14.650(2),c=27.42(2) (A), α=β=γ=90°, Z=4 V=3775.8A3, F(000)=1872.0, 2563 reflections collected and 1244 were used in the solution with R=0.058. The complex is an asymmetric dimer with a triple bridge comprising two dithiolate sulphurs and a nitrogen of the azide ligand. Convolution analysis of the cyclic voltammetric response of complex (1) confirmed a diffusion controlled one electron reversible reduction process.