Three coordinated first row-transition metal complexes, [M{N(SiMe3)2}3]−1/0: Structure, bonding, and magnetic properties

Abstract

Structure, bonding, and magnetic properties of [M{N(SiMe3)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 σ and π 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 NiII 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 CrII and MnIII 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 NiII complexes, the blocking barrier (Ueff) is found to be 127 cm−1. Thus, it has a high potential to be utilized as a single ion magnet (SIM).