(6666)MACROTETRACYCLIC 3D-ELEMENT METALCHELATES WITH TETRA[BENZO]PORPHYRAZINE AND TWO ACIDO-LIGANDS: QUANTUM-CHEMICAL CALCULATION BY USING DENSITY FUNCTIONAL THEORY

The parameters of molecular (bond lengths, bond and non-bond angles) and electronic (spin multiplicity of the ground state, charge distribution over individual atoms) (6666)macrotetracyclic chelates of 3d-elements (M), where M is Ti, V, Cr, Mn, Fe, Co, Ni, Cu, containing a tetradentate (NNNN)-donor atom ligand - tetra[benzo]porphyrazine ]tetra[benzo](18)tetraazaporphyrin(1.1.1.1)] and two axially oriented fluoride anions, are calculated using the density functional theory (DFT) in the B3PW91/TZVP version. It is found that all these chelate complexes have a pseudo-octahedral or close to it structure, where M is located in the plane of four donor nitrogen atoms. The lengths of M-N bonds, as well as the lengths of M-F bonds in most of these studied metal complexes, are equal to each other. All 5- and 6-membered cycles in each of these compounds are identical to each other both in the sum of the values of valence angles and in their set. The values of standard thermodynamic characteristics (enthalpy, entropy, and Gibbs energy) of the formation of these metal chelates are also determined.