The tightly cross-linked Mo3nSe3n+2 (n = 2, 3,...infinity) cluster compounds react with alkali metal cyanide or cyanide salt mixtures at temperatures of 450-675 degreesC to yield cyanide-terminated molybdenum chalcogenide clusters, [Mo6Se8(CN)(6)](n-) (1(n-)) (n = 6, 7) and [Mo4Se4(CN)(12)](8-) (2(8-)). The process by which discrete 1(n-) clusters are excised from a CN-linked intermediate chain compound, K6Mo6Se8(CN)(5) (3), was investigated, and the cubane cluster 2(7-) plays an essential role. An efficient one-step synthesis for Na-8[2(8-)] is presented. These clusters are stable in basic aqueous solutions. Cyclic voltammetric (CV) measurements in basic aqueous media show multiple reversible redox waves corresponding to 1(6-/7), 1(7-/8-), and 1(8-/9-) redox couples with half-wave potentials of E-1/2 = -0.442, -0.876, and -1.369 V, respectively, versus SHE. Half-wave potentials (E-1/2) for the [Mo4Se4(CN)(12)](6-/7-) and [Mo4Se4(CN)(12)](7-/8-) couples are 0.233 and -0.422 V, respectively, versus SHE. The 2(8-) compounds are K7Na[2(8-)].5H(2)O-MeOH, CS7Na4[2(8-)]Cl-3, Na-8[2(8-)], and K4Na4[2(8-)].12H(2)O. The products were characterized by X-ray crystallography, cyclic voltammetry, and UV-vis spectroscopy. Reduction potentials measured by voltammetry are consistent with conditions needed for isolating reduced species on a preparative scale but are much more negative than previously reported values. Na-8[1(8-)].20H(2)O was isolated by reduction of 1(7-) with Zn in aqueous NaCN solution. Reduction potentials measured in basic NaCN solutions of 2(8-) also differ widely from previous reported values.