Kinetics Aspects of the Reversible Assembly of Copper in Heterometallic Mo 3 CuS 4 Clusters with 4,4'-Di-tert-butyl-2,2'-bipyridine.

Treatment of the triangular [Mo3 S4 Cl3 (dbbpy)3 ]Cl cluster ([1]Cl) with CuCl produces a novel tetrametallic cuboidal cluster [Mo3 (CuCl)S4 Cl3 (dbbpy)3 ][CuCl2 ] ([2][CuCl2 ]), whose crystal structure was determined by X-ray diffraction (dbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine). This species, which contains two distinct types of Cu(I), is the first example of a diimine-functionalized heterometallic M3 M'S4 cluster. Kinetics studies on both the formation of the cubane from the parent trinuclear cluster and its dissociation after treatment with halides, supported by NMR, electrospray ionization mass spectrometry, cyclic voltammetry, and density functional theory calculations, are provided. On the one hand, the results indicate that addition of Cu(I) to [1]+ is so fast that its kinetics can be monitored only by cryo-stopped flow at -85 °C. On the other hand, the release of the CuCl unit in [2]+ is also a fast process, which is unexpectedly assisted by the CuCl2 - counteranion in a process triggered by halide (X- ) anions. The whole set of results provide a detailed picture of the assembly-disassembly processes in this kind of cluster. Interconversion between trinuclear M3 S4 clusters and their heterometallic M3 M'S4 derivatives can be a fast process occurring readily under the conditions employed during reactivity and catalytic studies, so their occurrence is a possibility that must be taken into account in future studies.