Abstract
AbstractThe benzene cation radicals [C6F5‐CF3]+, [1,4‐C6F4(CF3)2]+, [1,2,4,5‐C6H2Cl4]+, [C6F5‐C6F5]+, and [C6Br6]+ have been obtained as salts with fluoroarsenic and fluoroantimony counterions. Their structures have been obtained by single‐crystal structure determinations, and supported by ESR measurements and DFT calculations. [C6F5‐CF3]+, [1,4‐C6F4(CF3)2]+, and [1,2,4,5‐C6H2Cl4]+ have the predicted bisallyl type structure. [C6F5‐C6F5]+ can be described as having a quinoid form with a strengthened central C–C bond and a smaller dihedral angle as compared to the neutral C6F5‐C6F5. [C6Br6]+ is the missing link between [C6F6]+, [C6Cl6]+, and [C6I6]+. It has a Jahn–Teller distortion, though weaker than [C6F6]+ and [C6Cl6]+, in contrast to [C6I6]+, which remains in a regular hexagon structure.
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