The reaction system (NH4)(3)VS4/Ag(PPh3)(2)Cl/R(2)dtcNa in CH3CN was studied to afford two V2Ag1-2S4 cubanelike cluster compounds and a trinuclear V3O3S2 complex. (Et4N)[V2AgS4(Me(2)dtc)(2)(PPh3)]. 1/2CH(3)CN ([Et4N]1 . 1/2CH(3)CN) crystallizes In the monoclinic space group P2(1)/c with a = 10.525(3) Angstrom, b = 16.340(8) Angstrom, c = 26.834(8) Angstrom, beta = 101.28(2)degrees, and Z = 4. Complex (Et4N)(2)[V2Ag2S4(CS3)(2)(PPh3)(2)] ([Et4N](2)2) crystallizes in the monoclinic space group C2/c with a = 21.212(5) Angstrom, b = 20.100(4) Angstrom, c = 15.039(2) Angstrom, beta = 102.72(2)degrees, and Z = 4. A stepwise aggregate process including a dinuclear V2Y2(mu-S)(2) (Y = S, O) intermediate was suggested to explain the formation of 1, 2, and trinuclear anion [V3O(mu-O)(2)(mu-S)(2)(Et(2)dtc)(3)](-). Structural features of these complexes show that the V2Y2(mu-S)(2) moiety can be seen as an independent unit to combine with other metal ion(s). A complex containing the [V2O2(mu-S)(2)(Et(2)dtc)(2)](2-) (3) cluster anion was separated from a reaction system of (NH4)(3)VS4/PPh3/Et(2)dtcNa, and its solvate complex {(Et4N)(3)Na[V2O2(mu-S)(2)(Et(2)dtc)(2)](2)}(2) . 1/2CH(3)OH . H2O crystallizes in orthorhombic space group Pnn2 with a = 31.599(1) Angstrom, b = 17.228(5) Angstrom, c = 14.104(7) Angstrom, and Z = 2. Infrared frequencies at 844-970 cm(-1) were associated with a V = O stretching vibration. The V = O additional coordination to the other metal ion gives rise to the red shift of the frequency. Proton and V-51 NMR spectra exhibit a paramagnetic V-IV center existing in the trinuclear complex (Et4N)[V3O(mu-O)(2)(mu-S)(2)(Et(2)dtc)(3)] ([Et4N](4)) and d(1)-d(1) coupling of V-V of the V2Y2(mu-S)(2) moiety for these complexes. Two sets of the P-31 signals for 2 at 16.6-19.3 ppm with equal intensity are attributed to P-31-Ag-107 coupling and may well hide two V atoms in a similar environment. Cyclic voltammetries show some similar electrochemical behaviors between 3 and 4 indicated by a common couple at -0.7 V/-0.65 V and an oxidation peak at +0.7 to +0.6 V which are proposed to be due to redox in the V2O2(mu-S)(2) moiety.