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Quantitative Assessment of Metal-Ligand Bonding in Halide-Containing Terpyridine Pincer Complexes of Group 10 Metals
1Department of Chemistry, Faculty of Science, Malayer University, Malayer, Iran.
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 C2v symmetry through a1, a2, b1, and b2 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.
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