Adamantane-like Cluster Complexes of Mixed-Valent Copper−Copper and Nickel−Copper Thiolates

Square-planar copper(II) and nickel(II) derivatives of the cis-dithiolate N2S2 ligand bis(N,N‘-2-mercapto-2-methylpropyl)-1,5-diazocyclooctane, (bme*daco)M, nucleate four CuICl moieties, forming MII 2CuI 4S4 clusters with unusual triply bridging thiolates, μ3-SR, in the topological form of adamantane. As determined by X-ray crystallography, the (bme*daco)M (M = Cu or Ni) metallothiolate serves as a bidentate ligand that bridges four CuI ions, utilizing all lone pairs on sulfurs. Further characterization by electrochemical and electronic spectral measurements suggests greater electron delocalization in the all-copper complex as compared to the NiCu heterometallic complex. Mass spectral data imply that the mixed-metal NiII 2CuI 4S4 is more stable toward CuCl loss than CuII 2CuI 4S4, a result that is corroborated by extraction of CuI by 1,2-bis(diphenylphosphino)ethane in the latter but not the former.