PREPARATION AND PROPERTIES OF GROUP-13 (GA, IN, TL) HETEROMETALLIC SINGLE AND CORNER-SHARED DOUBLE CUBE DERIVATIVES OF [MO3S4(H2O)(9)](4+) AND RELATED STUDIES

New routes are described for the preparation of cuboidal complexes [Mo 3InS4(H2O)(12)](5+), [Mo3GaS4(H2O)(12)](5+), and [Mo6InS8(H2O)(18)](8) from the incomplete cuboidal [Mo3S4(H2O)(9)](4+). A comparison of th e aqueous solution properties of the single cubes, [Mo3GaS4(H2O)(12)]( 5+) and [Mo3InS4(H2O)(12)](5+), and the double cubes, [MO6InS8(H2O)(18 )](8+) and [Mo6TlS8(H2O)(18)](8+), the total listing of group 13 deriv atives, is reported. The single cube [Mo3InS4(H2O)(12)](5+) can be qua ntitatively converted into the double cube by reductive (H3PO2 or BH4- ) addition of [Mo3S4(H2O)(9)](4+). The double cubes are O-2 sensitive, much more so in HCl than Hpts (pts(-) = p-toluenesulfonate), and are oxidized by H+ in HCl solutions with the formation of H-2 (detected by gas chromatography). The single cubes are less reactive in air, and a re only oxidized by H+ at higher (similar to 4 M) levels. Stoichiometr y measurements with [Co(dipic)(2)](-) and [Fe(H2O)(6)](3+) as le(-) ox idants were used to confirm charges on the clusters. In the absence of reduction potentials, rate constants for outer-sphere [Co(dipic)(2)]( -) oxidations give a measure of redox properties. Oxidation of [Mo6InS 8(H2O)(18)](8+) with [Co(dipic)(2)](-) provides a route back to the si ngle cube [Mo(3)TnS(4)(H2O)(12)](5+). Properties of [W3InS4(H2O)(12)]( 5+) and [Mo6InO2S6(H2O)(18)](8+) obtained from [W3S4(H2O)(9)](4+) and [Mo3OS3-(H2O)(9)](4+) are also considered. The single cube [W3InS4(H2O )(12)](5+) is >10(3) times more reactive with [Co(dipic)(2)](-) than [ Mo3InS4(H2O)(12)](5+), consistent with reducing properties W > Mo. No evidence was obtained in these studies for [Mo3TlS4 (H2O)(12)](5+), [M o6GaS8(H2O)(18)](8+), or the recently proposed 6+ analogue of [Mo3GaS4 (H2O)(12)](5+).