Synthesis of dinuclear metal complexes of a macrocyclic ligand with multi-ligating pendant-arms. Crystal structures of its manganese(II) and cadmium(II) complexes
M. Qian et al., Synthesis of dinuclear metal complexes of a macrocyclic ligand with multi-ligating pendant-arms. Crystal structures of its manganese(II) and cadmium(II) complexes, INORG CHIM, 305(1), 2000, pp. 83-90
A series of dinuclear metal complexes, [M2L](ClO4)(2) (M = Mn2+, Ni2+, Zn2 and Cd2+), of a pendant-arm macrocyclic ligand (H2L) have been prepared vi
a the cyclocondensation between sodium 2,6-diformyl-4-chlorophenolate and N
-(2-methylenepyridinyl)tris(2-aminoethyl)ami and the subsequent transmetali
ation with metal perchlorates, and characterized spectroscopically. Among t
hese, the crystal and molecular structures of [Mn2L](ClO4)(2) and [Cd,L](Cl
O4)(2) have been determined by X-ray diffraction. The structure of the mang
anese complex indicates that each pendant-arm is bonded bidentately to the
adjacent metal atom and both arms are on the same side of the resulting tet
ra-imine macrocycle. The six-coordinated manganese ion has a distorted octa
hedral configuration in which an uncommon eight-membered chelating ring has
been formed due to the non-bonding tertiary nitrogen. In the structure of
the cadmium complex, the pendent arm binds in the same manner to the metal
as in the manganese complex. Each metal atom is coordinated by all the dono
r atoms including the tertiary nitrogen atom in one chamber of the macrocyc
le, and the cadmium ion is seven-coordinated with a geometry of a highly di
storted pentagonal bipyramid. The manganese(II) ions in the macrocycle are
both essential high spin, with only a very weak antiferromagnetic interacti
on. The manganese compound showed only a moderate activity in the catalytic
decomposition of hydrogen peroxide. (C) 2000 Elsevier Science S.A. All rig
hts reserved.