On the relation between carbonyl stretching frequencies and the donor power of chelating diphosphines in nickel dicarbonyl complexes

The relation between spectroscopic observables and the detailed metal–ligand bonding features in chelation complexes is addressed using both experimental and state-of-the-art theoretical and computational methods. We synthesized and characterized a set of six nickel dicarbonyl complexes of general formula [Ni(CO)2(PP)], where PP is an atropoisomeric chelating diphosphine ligand. The analysis of the obtained experimental data and the basicity and oxidative potentials of the free ligands suggests a close relation between the donor ability of the chelating ligand and the carbonyl stretching frequencies observed in the complexes. We then use theory to unravel the detailed mechanisms of chelation-bond formation in terms of partial charge flows between the molecular orbitals of the fragments. By extending the promising, recently published natural orbitals for chemical valence/charge displacement (NOCV/CD) analysis scheme we provide a thorough, quantitative description of the several charge fluxes following the metal–ligand bond formation and demonstrate that the carbonyl stretching frequencies in the considered complexes selectively respond to the s-donation charge flow from the phosphorus lone pairs of the ligands, with the frequency shift being in quantitative correlation with the extent of the ligand-to-metal charge transfer.