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

作者：Jose Juarez Perez Emilio; Aragoni M Carla; Arca Massimiliano; Blake Alexander J; Devillanova Francesco A; Garau Alessandra; Isaia Francesco; Lippolis Vito^*; Nunez Rosario; Pintus Anna; Wilson Claire

来源：Chemistry - A European Journal, 2011, 17(41): 11497-11514.

DOI：10.1002/chem.201100970

• charge transfer
• density functional calculations
• halogens
• hypervalent compounds
• oxidative addition
• selenium

The reactivity of the imidazoline-2-selone derivatives 1,1'-methylenebis(3-methyl-4-imidazoline-2selone) (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 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.

• 出版日期2011-10