Micera, Giovanni and Garribba, Eugenio (2010) Application of DFT methods in the study of VIVO2+–peptide interactions. European Journal of Inorganic Chemistry, Vol. 2010 (29), p. 4697-4710. eISSN 1099-0682. Article.
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VIVO2+ complexes formed by histidylglycylglycine (HisGlyGlyH), glycylglycylhistidine (GlyGlyHisH), glycylglycylcysteine (GlyGlyCysH2), N-glycyl-bis(imidazol-2-yl)methylamine (Gly–BIMA), N-glycyl-bis(pyridin-2-yl)methylamine (Gly–BPMA), salicylglycyl-L-alanine (SalGly-L-AlaH2) and 1,2-bis(2-hydroxybenzamido)benzene (H2hybeb) in their fully deprotonated form were studied by density functional theory (DFT) methods. They are characterised by different total electric charges, total equatorial charges and number of V–N–amide bonds. DFT calculations enable structural features, like V–donor bond lengths, and spectroscopic features, like electron paramagnetic resonance (EPR) and electronic absorption parameters, to be calculated. The results suggest that an amide group coordinates vanadium in the“amide-” rather than the “imine-like” form with the nitrogen atom negatively charged and with a double bond between the carbon and oxygen atoms of the carbonyl group, and that the equatorial charge is delocalised among all the donors bound to vanadium (Ooxido included). The analysis of the molecular orbital composition reveals that the dxy orbital is the vanadium orbital at lower energy, that it can participate in a π bond with the nitrogen pz orbital of the amide groups, that the vanadium dxz and dyz orbitals are involved in a large π interaction with the oxido px and py orbitals and that differences in the donor strengths of the ligands and deviations from the ideal square-pyramidal symmetry can result in the separation of the energies of the vanadium dxz and dyz orbitals.
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