Diorganotelluride···N Chalcogen Bonds: Analysis and Tuning of Two σ‐Holes

<jats:p>Organotellurium(II) compounds contain two σ‐holes that may be fine‐tuned through substituents. This work investigates the structural chemistry of two new chalcogen bond (ChB) aggregates of organotellurium(II) compounds and the strong bases 1,4‐diazabicyclo[2.2.2]octane (DABCO) and quinuclidine. Two different structural motifs were encountered: an oligomeric ChB aggregate between bis(pentafluorophenyl) telluride and the acceptor DABCO, in which each Te atom partakes in two short Te···N contacts, and a molecular adduct between the unsymmetrical (pentafluorophenyl)(phenyl) telluride and quinuclidine, in which only the more electrophilic σ‐hole forms the interaction. The latter ChB represents the shortest intermolecular Te···N contact characterized by diffraction methods. The calculated electron density of the compound was obtained using the experimentally established geometry, and the electrostatic potential of the ChB donor confirmed that electron‐withdrawing organic residues result in a more pronounced associated σ‐hole.</jats:p>