Synthesis and Characterization of 14-Membered Tetraaza Macrocycles with N-Ethyl Groups and their Nickel(￥±) and Copper(￥±) Complexes

摘要

The 14-membered tetraaza macrocyclic ligand 1,8-diethyl-5,12-dimethyl-1,4,8,11-tetraazacyclote tradeca-4,11-diene(B) can be synthesized as its dihydroperchlorate salt by the one-pot reaction of 2-ethylaminoethylamine, methylvinyl ketone, and perchloric acid in absolute ethanol. The reaction of Ni(ケ) or Cu(ケ) ion and the salt yields [M(B)]2+ (M = Ni(ケ) or Cu(ケ)), which reacts with NaBH4 to produce [M(D)]2+ (D = 1,8-diethyl-5,12-dimethyl-1,4,8,11-tetraazacyclote tradecane). The complexes [M(L)]2+ (L = B or D) have planar geometry and contain two ethyl groups at the donor nitrogen atoms of the ligands. The red solids [Cu(B)](X)2 (X = ClO4- or PF6-) react with water molecules of atmospheric moisture to produce the purple solids in which water molecules are coordinated to the metal ion. Synthesis, characterization, and the properties of the new N-ethylated macrocyclic ligands and their Ni(ケ) and Cu(ケ) complexes are reported.