Hypothesis of Hemoprotein Sensor Confirmed by Ab initio Quantum-Chemical Method

The nature of the chemical bond of complexes of iron and cobalt porphyrinates with ligands is studied by the quantum-chemical method in the Hartree–Fock self-consistent field approximation using the 3-21G basis set. The addition of oxygen molecule to the MP and MPIm complexes (M = Fe, Co; Im is imidazole) is established to be more favorable than water addition. However, imidazole, which is the second ligand in the MPImO₂ and MPImH₂O complexes (M = Fe, Co), increases the M–O₂ and M–H₂O binding energies for iron, but decreases them for cobalt. The Co atom is bound with the porphyrin ring more strongly than the iron atom due to the larger total overlap of the atomic orbitals. The calculations of the binding energy in the complexes demonstrate similar changes in the structures of the spatial conformation of the deoxy form (FeP + H₂O) of iron porphyrinate and the oxy form (CoP + O₂) of cobalt porphyrinate. This is an argument in favor of the hypothesis of hemoprotein sensor of partial oxygen stress in tissues.