ChemInform Abstract: Synthesis and Characterization of Novel Binuclear Copper(II) and Nickel(II) Complexes with N,N′,N′′,N′′′-Tetrakis(2-pyridylmethyl)-1,4,8,11-tetraazacyclotetradecane (tpmc) Containing Various Anions. X-Ray Analyses of (Cu2F(tpmc))(ClO4)3·2 CH3CN and (Cu2Cl(tpmc))(ClO4)3·H2O.
Abstract
The anion-bridged dicopper complexes (IIIa) (space group P21/n, Z=4) and (IIIc) are synthesized by reaction of the starting complex (I) with NaCl (II) or NaI or direct reaction of Cu(II) perchlorate with 0.5 equiv. of the macrocyclic title ligand and NaBr, NaN3, or NaNO2.
ChemInform Abstract
The anion-bridged dicopper complexes (IIIa) (space group P21/n, Z=4) and (IIIc) are synthesized by reaction of the starting complex (I) with NaCl (II) or NaI or direct reaction of Cu(II) perchlorate with 0.5 equiv. of the macrocyclic title ligand and NaBr, NaN3, or NaNO2. Using an excess of NaN3 or NaSCN, dicopper(II) complexes are formed in which an anion is singly coordinated to each Cu atom. Ni(II) perchlorate reacts with the title ligand to give a 2:1 complex isolated as a tetraperchlorate in two different forms (diamagnetic orange form with square-planar coordination and paramagnetic blue form with five-coordinated Ni ions). The formation constants for the reaction (I) + X- → (III) are determined spectrophotometrically. On the basis of electronic and IR spectra, stability constants, and magnetic moments it is assumed that the complexes (IIIc) have similar structures to those of (IIIa) and previously prepared (IIIb) (P21/a, Z=4). Their structures are determined by X-ray analysis.
