ortho-Carom-N bond fusion in aniline associated with electrophilic chlorination reactions at ruthenium(III) coordinated acetylacetonates

► An unprecedented oxidation of coordinated aniline to ortho-semidine by perchlorate anion is described. ► The reactions were followed thorough chemical as well as X-ray structure analyses of the complexes. ► Rational for the above chemical reactions have been proposed.