Nickel macrocyclic complexes with porphyrazine and some [benzo]substituted, oxo and fluoro ligands: DFT analysis

Abstract

By using quantum chemical calculation data obtained by the DFT method with the OPBE/TZVP and B3PW91/TZVP levels, the principal possibility of the existence of three heteroligand complexes of nickel, each of which was shown to contain in the inner coordination sphere either porphyrazine or di[benzo]- and tetra[benzo]porphyrazine, oxygen (O[Formula: see text] and fluorine (F[Formula: see text] ions. The data on the geometric parameters of the molecular structure of these complexes are presented; which shows that NiN4 chelate nodes, all metal-chelate and non-chelate cycles in each of these complexes, are strictly planar. The bond angles between two donor nitrogen atoms and a nickel atom are equal to 90[Formula: see text], while the bond angles between donor atoms N, Ni, and O or F, in most cases, albeit insignificantly, differ from this value. Nevertheless, the bond angles formed by Ni, O and F atoms are exactly 180[Formula: see text]. NBO analysis data for these complexes are presented; it was noted that the ground state of all these complexes was a spin doublet. It has been shown that a good agreement between the data obtained using the above two versions of the DFT method occurs. Also, standard thermodynamic parameters of formation (standard enthalpy [Formula: see text], entropy [Formula: see text] and Gibbs’s energy [Formula: see text] for the macrocyclic compounds under consideration were calculated.