The Construction of (N2S2)Ni−Pd Clusters: A Slant‐Chair, a Basket and a C4‐Paddlewheel Structure

In pursuit of an analogy between bidentate diphosphane ligands and cis‐dithiolato nickel complexes, the easily prepared [bis(mercaptoethane)diazacycloheptane]nickel complex, Ni‐1′, has been treated with PdII and NiII sources. With the latter, trinickel species are observed with typical slant‐chair structures; for palladium(II) chloride, a basket‐type structure is realized in which the floor of the basket is a PdS4 unit and the sides are N2S2 units. One chloride atom is held within the basket at a Pd···Cl distance of 3.26 Å. With Pd(NO3)2 as a palladium source, a hexanuclear aggregate in the form of a C4‐paddlewheel structure is obtained. In this structure, the N2S2Ni complex serves as a bidentate ligand which bridges two Pd2+ cations at a distance of 3.132 Å. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)