Enolate SNAr of unactivated arenes via [(η6-arene)RuCp]+ intermediates

A series of complexes of the general formula [(eta(6)-arene)RuCp][PF6] (where arene = aryl halides or nitroarenes) were synthesised and the arene ring was found to be reactive towards an intermolecular nucleophilic aromatic substitution (SNAr) reaction with a series of cyclic 1,3-diones. Competition experiments indicated that leaving group ability of the aryl halides and nitroarenes went in the order of F >> NO2 > Cl > Br. Following SNAr, the arene rings were liberated quantitatively via a rapid photolysis reaction (<15 min).

Automated summary

A series of complexes with the general formula [(eta(6)-arene)RuCp][PF6] were synthesized, and the reactivity of the arene ring towards intermolecular nucleophilic aromatic substitution (SNAr) reaction with cyclic 1,3-diones was studied. Competition experiments revealed the leaving group ability of the aryl halides and nitroarenes, with the order of F >> NO2 > Cl > Br. Rapid photolysis reaction freed the arene rings quantitatively after SNAr reaction (<15 min).