Isotopic Studies of the Metal–Ligand Bond. Part III. The Far Infrared Spectra of Some Tetragonal Diamine Complexes of Cobalt(II) and Nickel(II): Studies of the Metal–Nitrogen Bond, as a Function of Metal Ion and of Spin State

Abstract

The far infrared spectra of 35 complexes of the formula M(diamine)2X2 are reported where M = Co(II) and Ni(II), X = Cl−, Br−, I−, NO3−, SCN−, ClO4−, and AgI2− and the diamine is ethylenediamine or its N,N-symmetric or antisymmetrically substituted dimethyl or diethyl derivative. Isotopic substitution studies with 62Ni and with 2H are carried out with eleven characteristic complexes and assignments for the metal–nitrogen modes in both octahedral and square planar complexes so deduced. In most cases the appropriate number of metal–ligand modes, based on symmetry considerations, are observed. The variations in observed M—N frequencies are discussed in terms of the electronic and geometric factors previously utilized for the corresponding copper(II) complexes. In complexes containing the asymmetric ligands, stretching vibrations arising from the two types of metal–nitrogen bond can be separately identified. Isotopic studies of pairs of complexes containing the same ligand and metal ion but with the latter in alternate spin states are reported here for the first time. All of the cobalt(II) complexes and several of the nickel(II) complexes are reported here for the first time.