The sulfide-containing ligand 2,2'-thiobis(4-methyl-6-tert-butylphenol H(2)mbp(2)S, coordinates facially to vanadium forming six-coordinate alkoxide- (1) or hydroxide-bridged (2) dimers that have been structurally characterized. V-51 NMR indicates that structural isomers are present. Electrochemical studies indicate that the metal centers in 1 are strongly coupled (K-com approximate to 10(5)). The corresponding sulfoxide. H(2)mbp(2)SO, coordinates to vanadium(V) to form a six-coordinate complex with a 2:1 L:M stoichiometry. Under the conditions of this study, direct oxygenation of the coordinated sulfide in 1 and 2 has not been observed. Crystal data for 1 (C55H74O8S2V2): space group R-3, a 35.6184(2) Angstrom, b = 35.6184(2) Angstrom, c = 13.52170(10) Angstrom, alpha, beta = 90 degrees, gamma = 120 degrees, Z = 18. Crystal data for 2 (C26H35N2O4SV): space group P2(1)/n, a = 13.2894(2) Angstrom, b = 12.9652(2) Angstrom, c = 16.3639(2) Angstrom, alpha,gamma = 90 degrees, beta = 102.43 degrees, Z = 4. Crystal data for 3 (C50H70O7S2V): space group P-1, a = 9.1567(5) Angstrom, b = 13.9314(8) Angstrom, c = 19.7196(11) Angstrom, alpha = 79.1460(10)degrees, beta = 86.5840(10)degrees, gamma = 82.7570(10)degrees, Z = 2.