Two series of octahedral oxovanadium(IV) compounds, containing charged or neutral axial ligands, with the tetradentate amidate molecules Hcapca and H(2)capcah of the general formulae trans-[(VOX)-O-IV(capca)](0/4) (where X = Cl- (1 . CH2Cl2),SCN- (2), N-3 (3), CH3C- OO- (4), PhCOO (5), imidazole (6 . CH3NO2), and eta -nBuNH(2) (7)) and cis-[(VOX)-O-IV(Hcapcah)](0/4) where X= Cl- (8 . 0.5 CH2Cl2), SCN- (9), N-3(-) (10 . 2CH(3)OH), and imidazole (11)), were synthesized and characterized by X-ray crystallography (1 . CH3OH, 8 . CHCl3, 9 . 2 CH3CN, 10 . CH3CN and cis-[VO(imidazole)(Hcapcah)](+)) and continuous-wave electron paramagnetic resonance (cw EPR) spectroscopy. In addition to the synthesis, crystallographic and EPR studies, the optical, infrared and magnetic properties (room temperature) of these compounds are reported. Ab initio calculations were also carried out on compound 8 . CHCl3 and revealed that this isomer is more stable than the trans isomer, in good agreement with the experimental data. The cw EPR studies of compounds 1-5, that is, the (VO2+)-O-IV species containing monoanionic axial ligands, revealed a novel phenomenon of the reduction of their A, components by about 10% relative to the N-4 reference compounds ([(VO)-O-IV(imidazole)(4)](2+) and [(VO)-O-IV(2,2-bi-pyririne)(2)](2+), see reference ). In marked contrast, such a reduction is not observed in compounds 6 CH3NO2-11, which contain neutral axial ligands Based on the spin-Hamiltonian formalism a theoretical explanation is put forward according to which the observed reduction of A, is due to a reduction of the electron - nuclear dipolar coupling (P). The present findings bear strong relevance to cw EPR studies of oxovanadium(IV) in vanadoproteins, (VO2+)-O-IV-substituted proteins, and in (VO2+)-O-IV; model compounds, since the hyperfine coupling constant, A(2), has been extensive used as a benchmark for identification of equatorial-donor-atom sets in oxovanadium(IV) complexes.