The Nature of Nonclassical Carbonyl Ligands Explained by Kohn–Sham Molecular Orbital Theory

When carbonyl ligands coordinate to transition metals, their bond distance either increases (classical) or decreases (nonclassical) with respect to the bond length in the isolated CO molecule. C−O expansion can easily be understood by π‐back‐donation, which results in a population of the CO's π*‐antibonding orbital and hence a weakening of its bond. Nonclassical carbonyl ligands are less straightforward to explain, and their nature is still subject of an ongoing debate. In this work, we studied five isoelectronic octahedral complexes, namely Fe(CO)(6) (2+), Mn(CO)(6) (+), Cr(CO)(6), V(CO)(6) (−) and Ti(CO)(6) (2−), at the ZORA‐BLYP/TZ2P level of theory to explain this nonclassical behavior in the framework of Kohn–Sham molecular orbital theory. We show that there are two competing forces that affect the C−O bond length, namely electrostatic interactions (favoring C−O contraction) and π‐back‐donation (favoring C−O expansion). It is a balance between those two terms that determines whether the carbonyl is classical or nonclassical. By further decomposing the electrostatic interaction ΔV (elstat) into four fundamental terms, we are able to rationalize why ΔV (elstat) gives rise to the nonclassical behavior, leading to new insights into the driving forces behind C−O contraction.