Quantitative Assessment of Metal–Ligand Bonding in Halide‐Containing Terpyridine Pincer Complexes of Group 10 Metals

ABSTRACT This study investigates metal–ligand bonding in planar pincer complexes [(tpy)M(X)] + , where M is Ni(II), Pd(II), or Pt(II) and X is a halide, using DFT and energy decomposition analysis. It shows that electrostatic interactions dominate the overall stability, while interaction strength decreases from fluoride to iodide. Orbital interactions contribute significantly (44.4%–50.2%) to the total attraction and are analyzed in detail under C 2v symmetry through a 1 , a 2 , b 1 , and b 2 components, revealing different metal–ligand overlap patterns. σ‐type interactions are the main orbital contribution (62.7%–76.1%), followed by π interactions (19.4%–29.6%), including in‐plane and out‐of‐plane components. δ‐type interactions are minor (4.8%–7.7%) but arise from metal–ligand π* overlap. Charge transfer trends from ligand to metal correlate well with both electrostatic and total interaction energies, supporting a consistent bonding description across the series.