Preparation and Crystal Structures of Silver(I), Mercury(II), and Lead(II) Complexes of Oxathia-Tribenzo-Macrocycles

An investigation of the coordination behavior of sulfur-containing mixed-donor tribenzo-macrocycles L-1-L-3 (L-1: 20-membered O3S2, L-2: 20-membered O2S3, and L-3: 23-membered O4S2) with d(10)-metal (Ag+, Hg2+, and Pb2+) salts is reported. The X-ray structures of five complexes (1-5) with different structural types and stoichiometries, including mono- to dinuclear species have been determined. Reactions of L-2 and L-3 with the silver(I) salts (PF6- and SCN-) afforded two dinuclear 2:2 (metal-to-ligand) complexes with different arrangements: a sandwich-type cyclic dinuclear complex [Ag-2(L-2)(2)](PF6)(2)center dot 3CH(2)Cl(2) (1) and a linear dinuclear complex [Ag-2(L-3)(2)(SCN)(2)] (2), in which two monosilver(I) complex units are linked by an Ag-Ag contact. Reactions of L-1 and L-2 with mercury(II) salts (SCN- and Cl-) gave a mononuclear 1:1 complexes [Hg(L-1)(SCN)(2)] (3) and [Hg(L-2)Cl-2] (4) with anion coordination in both cases. L-2 reacts with lead(II) perchlorate to yield a mononuclear sandwich-type complex [Pb(L-2)(2)(ClO4)(2)] (5), giving an overall metal coordination geometry of eight with a square antiprism arrangement. From these results, the effects of the donor variation and the anion-coordination ability on the resulting topologies of the soft metal complexes are discussed.