A Dibismuthane with Olefin Functional Groups: Towards Tridentate Hybrid Chalcogen/Olefin Ligands

Abstract Bis[dibenzobismepine], a dibismuthane composed of two bismepine units (R 2 Bi−BiR 2 ), was synthesized and fully characterized (R 2 =(C 6 H 4 CH) 2 ). Reactions of this dibismuthane with diphenyl dichalcogenides, dibenzoylperoxide, and elemental chalcogens have been investigated. All products of these reactions have been isolated and fully characterized, including a series of compounds R 2 Bi−E−BiR 2 (E=O−Te). These species contain two olefin units of the bismepine moieties and a chalcogen atom as potential coordination sites. The potential of these species to act as hybrid tridentate chalcogen/olefin ligands with bismuth atoms as structure‐determining elements in the backbone has been investigated by theoretical approaches, aiming at the complexation of Co I , Rh I , Ir I and Ni 0 , Pd 0 , Pt 0 . The analytical techniques applied in this work include heteronuclear and 2D NMR spectroscopy, elemental analysis, single‐crystal X‐ray diffraction analysis, and DFT calculations.