Iron-Promoted CC Bond Formation in the Gas Phase

An unusual iron transfer and carbon-carbon coupling take place in gas-phase ionized mixtures containing ferrocene and dichloromethane. Ferrous chloride and the protonated benzenium ion are eventually formed by a thermal and efficient reaction, through stable intermediates that undergo a remarkable reorganization. The mechanism of the concerted iron extrusion, carbon-chlorine bond activation and carbon-carbon bond formation is elucidated by electronic structure calculations that show the crucial role of iron.