The synthesis, structure, and properties of (Me3NBz)2[V(S2)S2( SPh)] (1) and (Me3NBz)4[V2(S2)2(CS3)4] (2) are described. Compound 1 is produced via oxidation of V(III) by elemental sulfur in a reaction mixture comprising VC13, LiSPh, S, and NEt4Cl in a molar ratio of 1:7:3:2. Compound 1 reacts with excess CS2 to produce compound 2 in ca. 65% yield. Compound 1 crystallizes in monoclinic space group P2t/n with the following unit cell dimensions at -158 °C: a = 18.178 (8) A, b = 8.843 (2) A, c -18.852 (7) A, ß = 107.06 (2)°, and Z = 4. A total of 2807 unique reflections with F > 3.00a(F) were employed, and the structure solution was refined to conventional indices R and /?w of 5.65 and 5.63, respectively. The vanadium(V) center is ligated by three types of sulfur atoms, viz.one PhS", one persulfide (S2* 12~), and two sulfido (S2~); the coordination geometry is approximately tetrahedral, with the S22" considered as occupying one site. Compound 2 crystallizes in monoclinic space group P2\/c with the following unit cell dimensions at -114 °C: a = 20.978 (4) A, b = 13.384 (2) A, c = 21.613 (4) A, ß * 93.14 (l)e, and Z = 4. A total of 5651 unique reflections with F > 2.33a(F) were employed, and the structure solution was refined to conventional R and Rv indices of 6.32 and 6.75, respectively. The vanadium(IV) centers are bridged by two symmetry-related ?2: 2:µ2-822" ligands, and two bidentate chelating trithiocarbonate ligands complete the coordination sphere about each metal. The metal centers are eight-coordinate, and the coordination geometry is best described as distorted dodecahedral. The V-V distances in the two independent molecules present in the unit cell are 2.872 (6) and 2.841 (6) A, respectively, and the complex is diamagnetic. An EHMO calculation was performed in order to assess the extent of metal-metal bonding in 2. Comparisons with the more highly developed area of Mo/S chemistry are made. The terminal trithiocarbonate sulfur atoms of 2 are nucleophilic and can be alkylated with Mel to produce the neutral compound V2(S2)2(S2CSMe)4 (3) in high yield. Compound 3 reacts with secondary amines to form the dialkyldithiocarbamate compounds V2(S2)2(S2CNR2)4 (R = Et (4a); R = "Bu (4b)).Solution-phase and l3C NMR studies of dimers 2-4 indicate the presence of two isomers whose interconversion is slow on the NMR time scale. Solution-phase51V NMR data are reported for compounds 1-4 and are compared to literature values for other V/S complexes.
