The stability of weak fluorine bonds in homogeneous catalyst is studied at the ab initio level for an arylpyridine post‐metallocene complex. The Ti···F···Hβ interaction scheme, involving the agostic bond with titanium and the H‐bond with an Hβ in the growing chain, is found to be the the most stable one. A possible optimal overlap involving the fluorine lone pairs is proposed. This three‐center interaction could play a role in the inhibition of Hβ transfer to the metal or to the monomer in the termination reactions.
