The 55Mn hyperfine interaction has been analysed for MN/II/ complexes of the formula: I. Mn/dtch/ 2 - high-spin, S= 5 2 II. Mn/dtch/2/NO//Cl/ - low-spin, S= 1 2 , were dtch=dithiocarbamate, xanthate or thioxanthate ligand. The increasing π-acceptor properties of the ligands result in the decrease of isotropic hyperfine parameters K. This effect has been observed for both types of complexes. The axially symmetric hyperfine tensor depending on the π-properties of the ligands has been determined for the low-spin complexes. The spin polarization mechanism involving π-orbitals /xz,yz/ has been used for interpretation of the 14N superhyperfine tensor.