Direct observation of the wheland intermediate in electrophilic aromatic substitution. Reversible formation of nitrosoarenium cations

The Wheland intermediate in electrophilic aromatic nitrosation, viz. the ni trosoarenium sigma-complex, is directly observed by transient absorption sp ectroscopy. Femtosecond time-resolved laser experiments based on charge-tra nsfer photoexcitation of electron donor/acceptor (EDA) complexes of nitroso nium cation with various arenes reveal the ultrafast formation of nitrosobe nzenium to occur in less than 10 ps via the radical/radical coupling of are ne cation radicals and nitric oxide. The lifetimes of the sigma-complexes i n dichloromethane solution are strongly temperature dependent-varying from nanoseconds (T = 298 K) to microseconds (T = 195 K). Steady-state photolysi s of arene/NO+ complexes in n-BuCl glasses at T= 77 K leads to nitrosoareni um sigma-complexes which persist for several hours. Based on a reaction sch eme that includes an ultrafast equilibrium between the [ArH+.,NO.] radical pair and the nitrosoarenium sigma-complex, energy diagrams are constructed which establish the highly endergonic reaction profile of electrophilic aro matic nitrosations with the arene/nitrosonium pi-complex as the thermodynam ic sink.