title: Anionic substituent control of the electronic structure of aromatic nitrenes.
abstract: The electronic structures of phenylnitrenes with anionic π-donating substituents are investigated by using mass spectrometry and electronic structure calculations. Reactions of para-CH(2)(-)-substituted phenylnitrene, formed by dissociative deprotonation of p-azidotoluene, with CS(2) and NO indicate that it has a closed-shell singlet ground state, whereas reactions of p-oxidophenylnitrene formed by dissociative deprotonation of p-azidophenol indicate either a triplet ground state or a singlet with a small singlet-triplet splitting. The ground electronic state assignments based on ion reactivity are consistent with electronic structure calculations. The stability of the closed-shell singlet states in nitrenes is shown by Natural Resonance Theory to be very sensitive to the amount of deprotonated-imine character in the wave function, such that large changes in state energies can be achieved by small modifications of the electronic structure.
authors.affiliation: The Department of Chemistry, Purdue University, West Lafayette, Indiana 47907-2084, USA.
authors.forename: Nathan J
authors.initials: NJ
authors.lastname: Rau
authors.forename: Emily A
authors.initials: EA
authors.lastname: Welles
authors.forename: Paul G
authors.initials: PG
authors.lastname: Wenthold