Transmetalation in Phosphorus‐Nitrogen PN³P‐Pincer Complexes: Competitive Ligand‐Metal Affinity

Abstract Simple and straightforward thermodynamically controlled transmetalation of phosphorus‐nitrogen Zn complex to phosphorus‐nitrogen pincer cobalt and nickel complexes were demonstrated. All the transmetalation products were well characterized by SCXRD, HRMS (positive and negative mode), and NMR. B−H plots from UV‐Vis studies further justify the transmetalation process. Transmetalation results and DFT calculations established the thermodynamic stability of these three complexes in the order of Zn<Co<Ni. The Intrinsic Bond Strength Order, Electron localization function, CHELPG‐ESP charges, and Extended Charges Decomposition Analysis (ECDA) were applied to rationalize the reaction outcome.