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

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.