Mononuclear and Polynuclear Chain Complexes of a Series of Multinucleating N/S Donor Ligands

Abstract

AbstractWe have prepared a series of five ligands with potentially N,S‐bidentate chelating arms derived from 3‐[2‐(methylsulfanyl)phenyl]pyrazole linked to central aromatic spacers by methylene units. Complexes with a variety of architectures have been obtained, including simple mononuclear complexes and polynuclear chain complexes. The p‐xylyl‐spaced ligand L1 forms one‐dimensional helical coordination polymers with copper(I) and silver(I) ions. These polymers display interligand aromatic stacking interactions within each helical chain. The m‐xylyl‐spaced ligand L2 forms a coordination polymer with copper(I) but a mononuclear complex with the larger silver(I) ion in which the central phenyl ring is involved in an η1 π‐type Ag···C interaction with the AgI. The 3,3′‐biphenyl‐spaced ligand L3 also forms one‐dimensional polymers with silver(I) and copper(I) ions, but in this case the sequence of bridging ligands between one metal centre and the next follows a zig‐zag path rather than being helical. The 1,8‐naphthyl‐spaced ligand L4 only forms mononuclear complexes with copper(I) and silver(I) ions showing that this spacer is not large enough to enforce a bridging coordination mode. The three‐armed ligand L5, prepared from 2,4,6‐tris(bromomethyl)mesitylene, also forms a mononuclear complex with silver(I) ions, where one of the three arms is pendant. However, when excess silver(I) ions are present two of these mononuclear complexes can be assembled into the trinuclear complex [Ag3(L5)2](ClO4)3. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)