Mor-Dalphos-Pd (II) oxidative addition complexes and related NH3 adducts: Insights into bonding and nonbonding interactions

Abstract

The stabilizing effects and bonding properties of the Pd metallic center in [(κ 2-P,N-Mor-Dalphos)Pd(Ar)Cl] complexes and related NH 3 adducts were investigated by density functional theory (DFT), the intrinsic bond orbital (IBO) approach and the Su-Li energy decomposition method (Su-Li EDA). The IBO analysis showed that the P atom from the P,N-Mor-Dalphos structure has stabilizing contributions in all Pd-Cl and Pd-NH 3 bonds in the complexes. According to the Su-Li energy decomposition analysis, the main energy that drives the interaction between the [Mor-Dalphos-Pd(Ar)] moiety and Cl − is the electrostatic term, therefore, the electrostatic energy interaction between them might be an important factor for taking into account when designing other [Mor-Dalphos-Pd(Ar)]-Cl precatalysts.

Generalized Kohn‐Sham energy decomposition analysis and its applications

“…Metal‐ligand interactions play important roles in nanocrystals, molecular recognition, drug design, metalloprotein chemistry, and so on. Both GKS‐EDA and LMO‐EDA have been employed in the interpretations of various metal‐ligand interactions, which are not trivial tasks due to the inherent complexity of the arrangement of electrons in d‐ and f‐metal‐atom orbitals coupled with the various ligands.…”