Intricacies of ligand coordination in tricarbonylchromium(0) complexes with ortho‐ and para‐fluorobiphenyls

The steric and electronic factors that influence which of the two rings of a substituted biphenyl ligand coordinates to chromium are of interest and it has been suggested that haptotropic rearrangements within these molecules may be limited if the arene–arene dihedral angle is too large. Two tricarbonylchromium(0) complexes and their respective free ligands have been characterized by single‐crystal X‐ray diffraction. In the solid state, tricarbonyl[(1′,2′,3′,4′,5′,6′‐η)‐2‐fluoro‐1,1′‐biphenyl]chromium(0), [Cr(C₁₂H₉F)(CO)₃], (I), exists as the more stable isomer with the nonhalogenated arene ring ligated to the metal center. Similarly, tricarbonyl[(1′,2′,3′,4′,5′,6′‐η)‐4‐fluoro‐1,1′‐biphenyl]chromium(0) crystallizes as the more stable isomer with the phenyl ring bonded to the Cr⁰ center. The arene–arene dihedral angles in these complexes are 55.77 (4) and 52.4 (5)°, respectively. Structural features of these complexes are compared to those of the DFT‐optimized geometries of ten tricarbonyl[(η⁶‐C₆H₅)(4‐F‐C₆H₄)]chromium model complexes. The solid‐state structures of the free ligands 2‐fluoro‐1,1′‐biphenyl and 4‐fluoro‐1,1′‐biphenyl, both C₁₂H₉F, exhibit arene–arene dihedral angles of 54.83 (7) and 0.71 (8)°, respectively. The molecules of the free ligands occupy crystallographic twofold axes and exhibit positional disorder. Weak intermolecular C—H…F interactions are observed in all four structures.