Three coordinated first row-transition metal complexes, [M{N (SiMe 3 ) 2 } 3 ]-1/0: Structure, bonding, and magnetic properties

Structure, bonding, and magnetic properties of [M{N(SiMe 3 ) 2 } 3 ] - 1/0 (M = first row-transition metal, Sc-Cu in + 2/+3 oxidation state) complexes are studied. The atoms in molecules (AIM) analysis shows that non-covalent interactions between the methyl hydrogens are prevalent. Energy decomposition analysis coupled with natural orbital for chemical valence (EDA-NOCV) analysis shows that the ligand is bonded to the metal ions through sigma and pi bonding. In addition, the reasonable contribution from the dispersion interaction supports van der Waals ' type of interaction. The highest value of magnetic anisotropy ( D ) is calculated in the Ni II complex with a value of -382.945 (-234.145) cm -1 at the CASSCF (NEVPT2) level of theory. It is significantly higher than the previously reported values of -14.644 (-15.631) and -63.691 (-64.000) cm -1 in similar Cr II and Mn III complexes, respectively. Ab Initio Ligand Field Theory (AILFT) is utilized to calculate the splitting of the d-orbitals in all the metal complexes. In the Ni II complexes, the blocking barrier ( U eff ) is found to be 127 cm -1 . Thus, it has a high potential to be utilized as a single ion magnet (SIM).