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

摘要

An investigation of the coordination behavior of sulfur-containing mixed-donor tribenzo-macrocycles L1-L3 (L1: 20-membered O3S2, L2: 20-membered O2S3, and L3: 23-membered O4S2) with d10-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 L2 and L3 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 [Ag2(L2)2](PF6)2·3CH2Cl2 (1) and a linear dinuclear complex [Ag2(L3)2(SCN)2] (2), in which two monosilver(I) complex units are linked by an Ag-Ag contact. Reactions of L1 and L2 with mercury(II) salts (SCN− and Cl−) gave a mononuclear 1:1 complexes [Hg(L1)(SCN)2] (3) and [Hg(L2)Cl2] (4) with anion coordination in both cases. L2 reacts with lead(II) perchlorate to yield a mononuclear sandwich-type complex [Pb(L2)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 anioncoordination ability on the resulting topologies of the soft metal complexes are discussed.