Preparation and Spectroscopic Properties of Manganese(II), Chloroiron(III), Cobalt(II), Nickel(II), Copper(II), Zinc(II), and Cadmium(II) Complexes with Hemiporphyrazine

Abstract

Abstract The manganese(II), chloroiron(III), cobalt(II), nickel(II), copper(II), zinc(II), and cadmium(II) complexes of 5,26:13,18-diimino-7,11:20,24-dinitrilodibenzo[c, n]-l,6,12,17-tetraazacyclo-docosine were prepared and studied by electronic, vibrational, ESR, and ESCA spectroscopy. The metal complexes assume the square-planar configuration types since the ligand field bands were not detected in the region of the 11600-18000 cm−1. A strong band due to the stretching mode of the C=N bond at 1665 cm−1 was shifted to lower frequency upon metal-coordination. ESCA spectra show that there are two kinds of nitrogen atoms in the present metal-free macrocycle and that upon complex formation the eight nitrogens are chemically equivalet in these complexes. Judging from the small Att vaule, the copper(II) complex presumes an essentially planar coordination with distortion toward tetrahedron.