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

ABSTRACT: 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

SUBMITTER: van der Lubbe SCC 

PROVIDER: S-EPMC7756819 | biostudies-literature | 2020 Dec

REPOSITORIES: biostudies-literature