American Chemical Society
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A Complete Family of Isostructural Cluster Compounds with Cubane-like M3S4M‘ Cores (M = Mo, W; M‘ = Ni, Pd, Pt):  Comparative Crystallography and Electrochemistry

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posted on 2003-01-30, 00:00 authored by Konrad Herbst, Piero Zanello, Maddalena Corsini, Nicola D'Amelio, Lutz Dahlenburg, Michael Brorson
By reaction of the geometrically incomplete cubane-like clusters [(η5-Cp‘)3Mo3S4)][pts] and [(η5-Cp‘)3W3S4][pts] (Cp‘ = methylcyclopentadienyl; pts = p-toluenesulfonate) with group 10 alkene complexes, three new heterobimetallic clusters with cubane-like cluster cores were isolated:  [(η5-Cp‘)3W3S4M‘(PPh3)][pts] ([5][pts], M‘ = Pd; [6][pts], M‘ = Pt); [(η5-Cp‘)3Mo3S4Ni(AsPh3)][pts] ([7][pts]). The compounds [5][pts]−[7][pts] are completing the extensive series of clusters [(η5-Cp‘)3M3S4M‘(EPh3)][pts] (M = Mo, W; M‘ = Ni, Pd, Pt; E = P, As) which allows the consequences of replacing a single type of atom on structural and NMR and UV/vis spectroscopic as well as electrochemical properties to be determined. Single-crystal X-ray structure determinations of [5][pts]−[7][pts] revealed that [5][pts] was not isomorphous to the other members of the series [(η5-Cp‘)3M3S4M‘(EPh3)][pts] due to distinctly different cell parameters, which in the molecular structure of [5]+ is reflected in a slightly different orientation of the PPh3 ligand. Electrochemical measurements on the series showed that the Mo-based clusters were more difficult to oxidize than their W-based analogues. The Pd-containing clusters underwent two-electron oxidation processes, whereas the Ni- and Pt-containing clusters underwent two separated one-electron oxidation processes.