Syntheses and crystal structures of manganese, nickel and zinc chloride complexes with dimethoxyethane and di(2-methoxyethyl) ether

Reactions of manganese and zinc chloride with dimethoxyethane (DME) in the presence of (CH3)3SiCl and water resulted in [MnCl2(DME)]n (1) with a polymeric chain structure and in the molecular [ZnCl2(DME)]2 (2), respectively. The complexes 1 and 2 reacted with di(2-methoxyethyl) ether (abbreviated diglyme) in tetrahydrofuran (THF) solvent achieving binuclear [MnCl2(diglyme)]2 (3) and mononuclear [ZnCl2(diglyme)] (4), respectively. The complex [NiCl2(diglyme)]2 (5) was prepared by the reaction of nickel chloride hexahydrate, diglyme and (CH3)3SiCl in THF solvent. A distorted octahedral geometry was found for manganese and nickel ions in the complexes 1, 3 and 5. Linear chains of manganese ions linked by double chloride bridges are present in 1. Two bridging chlorides connect two manganese or nickel atoms into isostructural binuclear molecules 3 and 5, respectively. Two zinc ions in the complex 2 are in different environments, in a tetrahedral and in an octahedral one, while five-coordinate zinc ions are present in the mononuclear complexes 4.

Binuclear [ZnCl2(DME)]2 versus mononuclear [ZnCl2(diglyme)] and polymeric [MnCl2(DME)]n versus binuclear [MCl2(diglyme)]2 (M = Mn, Ni) demonstrate the effect of ethereal ligands on the nuclearity of the transition–metal complexes.Figure optionsDownload as PowerPoint slide