Preparation and Properties of Group 13 (Ga, In, Tl) Heterometallic Single and Corner-Shared Double Cube Derivatives of [Mo(3)S(4)(H(2)O)(9)](4+) and Related Studies.

New routes are described for the preparation of cuboidal complexes [Mo(3)InS(4)(H(2)O)(12)](5+), [Mo(3)GaS(4)(H(2)O)(12)](5+), and [Mo(6)InS(8)(H(2)O)(18)](8+) from the incomplete cuboidal [Mo(3)S(4)(H(2)O)(9)](4+). A comparison of the aqueous solution properties of the single cubes, [Mo(3)GaS(4)(H(2)O)(12)](5+) and [Mo(3)InS(4)(H(2)O)(12)](5+), and the double cubes, [Mo(6)InS(8)(H(2)O)(18)](8+) and [Mo(6)TlS(8)(H(2)O)(18)](8+), the total listing of group 13 derivatives, is reported. The single cube [Mo(3)InS(4)(H(2)O)(12)](5+) can be quantitatively converted into the double cube by reductive (H(3)PO(2) or BH(4)(-)) addition of [Mo(3)S(4)(H(2)O)(9)](4+).

Preparation and Solution Properties of Chalcogenide-Rich Clusters [Mo(3)Y(7)(H(2)O)(6)](4+) (Y = S, Se): Kinetics of PR(3)(3-) Abstraction of Y from &mgr;-(Y(2)(2-)) and H(2)O Substitution by Cl(-) and Br(-).

The chalcogenide-rich trinuclear Mo(IV)(3) clusters [Mo(3)Y(7)(H(2)O)(6)](4+), containing single &mgr;(3)-(Y(2)(-)) and three &mgr;-(Y(2)(2)(-)) core ligands, have been obtained for the first time from polymeric {Mo(3)Y(7)Br(4)}(x)() via [Mo(3)Y(7)Br(6)](2)(-) (Y = S, Se). ICP analyses of 2 M HCl solutions give Mo:S and Mo:Se ratios consistent with the formulas indicated, and on reaction with concentrated HBr, 85% recovery of (Et(4)N)(2)[Mo(3)S(7)Br(6)], the structure of which is known, has been achieved. Abstraction of S and Se with PPh(3) (two-phase system), or the water-soluble phosphine (3-SO(3)C(6)H(4))(3)P(3)(-) (PR(3)(3)(-)), gives quantitative formation of [Mo(3)S(4)(H(2)O)(9)](4+) and [Mo(3)Se(4)(H(2)O)(9)](4+).

Preparation and Properties of the Corner-Shared Double Cube [Mo(6)BiS(8)(H(2)O)(18)](8+) as a Derivative of [Mo(3)S(4)(H(2)O)(9)](4+) in Aqueous Acidic Solutions.

The reaction of [Mo(3)S(4)(H(2)O)(9)](4+) with Bi(III) in the presence of BH(4)(-) (rapid), or with Bi metal shot (3-4 days), gives a heterometallic cluster product. The latter has been characterized as the corner-shared double cube [Mo(6)BiS(8)(H(2)O)(18)](8+) by the following procedures. Analyses by ICP-AES confirm the Mo:Bi:S ratio as 6:1:8.

Aqueous Solution Chemistry of the Mo(3)PdS(4) Cube: Substitution Reactions and the Double to Single Cube Interconversion Induced by CO, Two Phosphines, Cl(-), Br(-), and NCS(-).

The kinetics of conversion of an edge-linked double cube, in this case [{Mo(3)PdS(4)(H(2)O)(9)}(2)](8+), to the corresponding single cube [Mo(3)(PdX)S(4)(H(2)O)(9)](4+), has been studied for the first time. Reaction is induced by six reagents X = CO, two water-soluble phosphines, Cl(-), Br(-), and NCS(-), which complex at the tetrahedral Pd. The first stage of reaction is fast and is accompanied by color changes, e.

Ligand Substitution Reactions at the Nickel of [Mo(3)NiS(4)(H(2)O)(10)](4+) with Two Water Soluble Phosphines, CO, Br(-), I(-), and NCS(-) and the Inertness of the 1,4,7-Triazacyclononane (L) Complex [Mo(3)(NiL)S(4)(H(2)O)(9)](4+).

Comparisons (25 degrees C) are made of substitution reactions, X replacing H(2)O, at the tetrahedral Ni of the heterometallic sulfido cuboidal cluster [Mo(3)NiS(4)(H(2)O)(10)](4+), I = 2.00 M (LiClO(4)). Stopped-flow formation rate constants (k(f)/M(-)(1) s(-)(1)) for six X reagents, including two water soluble air-stable phosphines, 1,3,5-triaza-7-phosphaadamantane PTA (119) and tris(3-sulfonatophenyl)phosphine TPPTS(3)(-) (58), and CO (0.