Detailed Density Functional Theory Study of the Cationic Zirconocene Compound [Cp(C₅H₄CMe₂C₆H₄F)ZrMe]

Detailed density functional theory studies at the B3LYP and PBE-D3 levels of theory were performed on the cationic compound [Cp(C₅H₄CMe₂C₆H₄F)ZrMe]⁺, with the F atom occupying either the ortho, meta, or para positions of the arene ring. In all cases, the arene ring coordinates with the cationic zirconium metal. The nature of this coordination is such that for the meta- or para-substituted arene ring, it is predominantly the ortho carbon atom of the C-H bond which interacts with the metal, as evident from noncovalent interaction studies. This is further corroborated by the natural bond orbital and quantum theory of atoms in molecular studies. In the case of the F atom being in the ortho position, we obtained clear-cut evidence for a Zr-F coordination.