Role of the Solvent in the Reactivity of Bis-4-imidazoline-2-selone Derivatives toward I 2 : An Experimental and Theoretical Approach.

The reactivity of 1,1'-bis(3-methyl-4-imidazolin-2-selone)methane ( L1 ) and 1,2-bis(3-methyl-4-imidazolin-2-selone)ethane ( L2 ) toward I ₂ has been explored in MeCN under different experimental conditions and compared with that in CH ₂ Cl ₂ . The compounds [ L1' ](I) ₂ ( I ), [ L1 I] _n (I) _n ( II ), [ L1 (μ-Se)](I) ₂ ·1/2H ₂ O ( III ), [ L1 I](I ₃ )·2I ₂ ( IV ), and [ L2 ](I) ₂ ·MeCN ( V ) were obtained and characterized. X-ray diffraction analyses point out an ionic nature for these compounds, which is presumably favored by the polarity of the solvent used. In particular, [ L1 I] _n (I) _n ( II ) represents the first example of an iodonium complex of imidazoline-2-selone derivatives, while [ L1 (μ-Se)](I) ₂ ·1/2H ₂ O ( III ) represents a unique example of a dicationic [RSeSeSeR] triselane. Density functional theory calculations have allowed us to better understand the nature of the obtained compounds and to justify their formations in polarizing reaction conditions rather than in low polar solvents.