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

Abstract

Abstract 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 Pd II and Ni II 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 PdS 4 unit and the sides are N 2 S 2 units. One chloride atom is held within the basket at a Pd ··· Cl distance of 3.26 Å. With Pd(NO 3 ) 2 as a palladium source, a hexanuclear aggregate in the form of a C 4 ‐paddlewheel structure is obtained. In this structure, the N 2 S 2 Ni complex serves as a bidentate ligand which bridges two Pd 2+ cations at a distance of 3.132 Å. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)