Issue 6, 2004

Aqueous solution chemistry of [Mo3CuSe4]n+ (n = 4, 5) and [W3CuQ4]5+ (Q = S, Se) clusters

Abstract

The triangular cluster [Mo3Se4(H2O)9]4+ reacts with Cu turnings to give a new heterometallic cuboidal cluster [Mo3CuSe4(H2O)10]4+ (purple; UV/Vis λ(ε): 352(3907), 509(2613)). The reaction of [Mo3Se4(H2O)9]4+ with CuCl afforded the 5+ cube [Mo3CuSe4(H2O)10]5+ (red; UV/Vis λ(ε): 356(5406), 500(3477)). In contrast, [W3Se4(H2O)9]4+ both with Cu and CuCl gives the 5+ cube, [W3CuSe4(H2O)10]5+ (yellow–green; UV/Vis λ(ε): 312(5327), 419(3256) and 628(680)). Cyclic voltammetry of [M3CuQ4(H2O)10]5+ in 2 M HCl (M = Mo, W; Q = S, Se) shows a reversible one-electron reduction wave for the Mo clusters, but no reduction occurs for the W clusters prior to H+ reduction. In HCl solutions, Cl is coordinated to the Cu site of the clusters, alongside some less extensive coordination to Mo and W, and for [W3(CuCl)S4(H2O)6Cl3]+, isolated as the supramolecular adduct with cucurbit[6]uril, [W3(CuCl)S4(H2O)6Cl3]2Cl2·C36H36N24O12·12H2O, the crystal structure was determined (Cu–W 2.856(4) Å, W–W 2.7432(15) Å, Cu–Cl 2.167(13) Å).

Graphical abstract: Aqueous solution chemistry of [Mo3CuSe4]+ (n = 4, 5) and [W3CuQ4]5+ (Q = S, Se) clusters

Supplementary files

Article information

Article type
Paper
Submitted
09 Oct 2003
Accepted
30 Jan 2004
First published
10 Feb 2004

Dalton Trans., 2004, 847-851

Aqueous solution chemistry of [Mo3CuSe4]n+ (n = 4, 5) and [W3CuQ4]5+ (Q = S, Se) clusters

R. Hernandez-Molina, M. Sokolov, P. Esparza, C. Vicent and R. Llusar, Dalton Trans., 2004, 847 DOI: 10.1039/B401386G

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