Unsupported Lanthanide-Transition Metal Bonds: Ionic vs Polar Covalent?

Lanthanide-transition metal complexes continue to be of interest, not only because of their synthetic challenge but also of their promising magnetic properties. Computational work examining the chemical bonding between lanthanides and transition metals in PyCp₂Ln-TMCp(CO)₂ (DyPyCp₂^2- = [2,6-(CH₂C₅H₃)₂C₅H₃N]^2-) reveals strong Ln-TM dative bonds. Gas-phase optimized geometries are in good agreement with experimental structures at the density functional theory (DFT) level with large-core pseudopotentials. From La to Lu, there is a small increase in the bond dissociation energy, as well as a decrease in Ln-Fe bond lengths. Energy decomposition analyses attribute this trend to an increase in the electrostatic contribution from the decreasing bond length and a modest increase in the orbital contribution. The natural bond orbital analysis clearly indicates that 3d⁶ "lone pairs" in the [FeCp(CO)₂]^- fragment act as a Lewis bases donating nearly 0.5 electron to Ln virtual orbitals of mainly d character. The interfragment bonding was also quantified by the quantum theory of atoms in molecules, which indicates that the Ln-Fe bond is more covalent than the Ca-Fe bond in the hypothetical CpCa-FeCp(CO)₂ but less covalent than the Zn-Fe bond in the hypothetical CpZn-FeCp(CO)₂. Further comparisons suggest that to the [PyCp₂Ln]⁺ cation the [FeCp(CO)₂]^- anion appears much like a halide. Overall, these Ln-TM dative bonds appear to have strong electrostatic contributions as well as significant orbital mixing and dispersion contributions.