Heteroligand Iron(V) Complexes Containing Porphyrazine, trans -Di[benzo]porphyrazine or Tetra[benzo]porphyrazine, Oxo and Fluoro Ligands: DFT Quantum-Chemical Study.

By using quantum chemical calculation data obtained by the DFT method with the B3PW91/TZVP and OPBE/TZVP levels, the possibility of the existence of three Fe(V) complexes, each of which contains in the inner coordination sphere porphyrazine/ trans -di[benzo]porphyrazine/tetra[benzo]porphyrazine (phthalocyanine), oxygen (O 2- ) and fluorine (F - ) ions, was shown. Key geometric parameters of the molecular structure of these heteroligand complexes are given; it is noted that FeN4 chelate nodes, and all metal-chelate and non-chelate cycles in each of these compounds, are practically planar with the deviation from coplanarity, as a rule, by no more than 0.5°. Furthermore, the bond angles between two nitrogen atoms and an Fe atom are equal to 90°, or less than this by no more than 0.1°, while the bond angles between donor atoms N, Fe, and O or F, in most cases, albeit insignificantly, differ from this value. Nevertheless, the bond angles formed by Fe, O and F atoms are exactly 180°. It is shown that good agreement occurs between the structural data obtained using the above two versions of the DFT method. NBO analysis data for these complexes are presented; it is noted that, according to both DFT methods used, the ground state of the each of three complexes under consideration may be a spin quartet or spin doublet. Additionally, standard thermodynamic parameters of formation (standard enthalpy ∆ f H 0 , entropy S 0 and Gibbs's energy ∆ f G 0 ) for the macrocyclic compounds under consideration are calculated.