Macrocyclic complexes derived from the cyclocondensation of sodium 2,6-diformyl-4-substituted phenolates with N,N-bis(2-aminoethyl)-2-hydroxybenzylamine and in situ transmetallation. An anticipated dinuclear Cd(II) pendant-arm macrocyclic complex and

摘要

The reaction between sodium 2,6-diformyl-4-X-phenolates (X=Me, Cl) and N,N-bis(2-aminoethyl)-2-hydroxybenzylamine (ahba) followed by in situ transmetallation of Cd(II)(ClO_4)_2 or Fe(III)(ClO_4)_3 resulted in the produced of a dinuclear Cd(II) pendant-arm macrocyclic complex and a mononuclear Fe(III) macrocyclic complex, respectively. Two complexes as well as the pro-amine, N,N-bis[N'-(salicylicdene)ethylimino]-N-methylphenolicamine (p-sema), have been crystallographically determined. In the cadmium complex, two metal atoms were bridged by two #mu#-phenoxy oxygen atoms of the tetra-imine macrocycle, and each Cd(II), located in a highly distorted octahedral hemisphere, is six-coordinated by two imine nitrogen atoms, one tertiary nitrogen atom and a pendant phenol moiety apart from two oxygen atoms. In the iron complex, an aryl group removed from the amine and a ring contraction occurring at one side arm during the reaction have led to the generation of a mononuclear Fe(III) complex, in which the six-coordinate metal atom has a distorted octahedral geometry of coordination. The pro-amine is a tripodal tertiary amine, which contains a 2-hydroxybenzyl group as one of the pods, apart from two salicylic Schiff base moieties as the other, two. The investigation of the magnetic moment nd the Mossbauer spectrum of the iron complex at room temperature has shown that Fe(III) is in a high-spin state.