Intercluster exchanges leading to hydride-centered bimetallic clusters: a multi-NMR, X-ray crystallographic, and DFT study

Encouraged by the successful syntheses of alloy nanoclusters (or nanoparticles) via intercluster (or interparticle) reactions, herein we apply this methodology to prepare a series of bimetallic hydride clusters. Mixing of two clusters, [Ag₇(H){E₂P(OⁱPr)₂}₆] (E = S, 1; Se, 3) and [Cu₇(H){E₂P(OⁱPr)₂}₆] (E = S, 2; Se, 4), yields two series of hydride-centered bimetallic clusters, [Cu_xAg_7-x(H){E₂P(OⁱPr)₂}₆] (x = 0-7; E = S, 5; Se, 6). Their compositions are fully characterized by positive-mode ESI-MS spectrometry, multi-NMR spectroscopy, and the structures of [Cu₆Ag(H){S₂P(OⁱPr)₂}₆] (5a) and [CuAg₆(H){Se₂P(OⁱPr)₂}₆] (6a) by single crystal X-ray diffraction. The presence of individual compounds in solution is the result of a (dynamic) chemical equilibrium primarily driven by metal exchanges. In fact, the process of inter-cluster exchange of 1 and 2 leading to hydride-centered bimetallic clusters 5 can be monitored by concentration-dependent ³¹P NMR spectroscopy of which the higher concentration of 1 in the reaction, the closer to its resonance will be the distribution, in accord with Le Chatelier's principle. The dynamic equilibrium is further confirmed by 2D exchange spectroscopy that reveals a stepwise process involving one metal exchange at a time. DFT calculations on a model series of clusters 6 show that silver prefers occupying the inner tetrahedral positions, while copper favors capping positions, in full agreement with the crystal structure of 5a and 6a.