A Unique Case of Oxidative Addition of Interhalogens IX (X=Cl, Br) to Organodiselone Ligands: Nature of the Chemical Bonding in Asymmetric ISeX Polarised Hypervalent Systems

The reactivity of the imidazoline‐2‐selone derivatives 1,1′‐methylenebis(3‐methyl‐4‐imidazoline‐2‐selone) (D1) and 1,2‐ethylenebis(3‐methyl‐4‐imidazoline‐2‐selone) (D2) towards the interhalogens IBr and ICl has been investigated in the solid state with the aim of synthesising “T‐shaped” hypervalent chalcogen compounds featuring the extremely rare linear asymmetric IEX moieties (E=S, Se; X=Br, Cl). X‐ray diffraction analysis and FT‐Raman measurements provided a clear indication of the presence in the compounds obtained of discrete molecular adducts containing ISeBr and ISeCl hypervalent moieties following a unique oxidative addition of interhalogens IX (X=Cl, Br) to the organoselone ligands. In all asymmetric hypervalent systems isolated, a strong polarisation was observed, with longer bond lengths at the selenium atom involving the most electronegative halogen. A topological electron density analysis on model compounds based on the quantum theory of atoms‐in‐molecules (QTAIM) and electron localisation function (ELF) established the three‐centre–four‐electron (3c–4e) nature of the bonding in these very polarised selenium hypervalent systems and new criteria were suggested to define and ascertain the hypervalency of the selenium atoms in these and related halogen and interhalogen adducts. “T‐shaped” adducts! Unprecedented “T‐shaped” adducts featuring ISeX moieties (X=Cl, Br) have been obtained from the oxidative addition of interhalogens IX to organoselone donors (see figure). Atoms‐in‐molecules and electron localisation function topological approaches were used to ascertain the hypervalent nature of the chalcogen atom in these unusual three‐body systems. New criteria for analysing the hypervalency in these and related systems are proposed.