N-methyl-N-phenylnitrenium ion from photolysis ofN-(methylphenylamino)-2,4,6-trimethylpyridinium tetrafluoroborate

Singlet−Triplet Splittings and 1,2-Hydrogen Shift Barriers for Methylphenylborenide, Methylphenylcarbene, and Methylphenylnitrenium in the Gas Phase and Solution. What a Difference a Charge Makes

“…The relaxation of the electronic wave function accounts for 5.1 kcal/mol of the reduction, while the geometric relaxation, in spite of the rather large change in C−H and N−H bond lengths, accounts for only 0.7 kcal/mol. The resulting low barrier in acetonitrile is consistent with the experimental observation of products arising from 1,2-hydrogen migration when alkylarylnitrenium ions are generated in acetonitrile solution . While not explicitly addressed here, we speculate that similar effects are operative in 1,2-alkyl migrations in substituted nitrenium ions, these migrations being better studied experimentally for reasons outlined in the introduction. , …”

“…The resulting low barrier in acetonitrile is consistent with the experimental observation of products arising from 1,2-hydrogen migration when alkylarylnitrenium ions are generated in acetonitrile solution. 67 While not explicitly addressed here, we speculate that similar effects are operative in 1,2-alkyl migrations in substituted nitrenium ions, these migrations being better studied experimentally for reasons outlined in the introduction. 53,98 The coupling of the solvation and relaxation effects in stabilizing 3 + q relative to 3 + S results from the high dielectric constant of acetonitrile ( ) 37.5 99 ).…”

Photogenerated N-Methyl-N-1-naphthylnitrenium Ion: Laser Flash Photolysis, Trapping Rates, and Product Study

“…All of the products are consistent with the formation of an arylnitrenium ion. Photoproducts 7 and 8 are formed through the nucleophilic addition of chloride at the ortho and para positions to the nitrogen and are analogous to adducts of similar arylnitrenium ions such as N -methyl- N -phenylnitrenium ion …”

“…Product 4 could occur through hydrogen abstraction from the solvent or through secondary photolysis/electron-transfer pathway of either of the chloro adducts . The 4-chloro or 2-chloro adduct may be irradiated to homolytically cleave the C−Cl bond.…”

The 1,2,4-Triazolyl Cation: Thermolytic and Photolytic Studies

“…While aromatic radical cations are stabilized by HFIP 24b,c because hydrogen-atom abstraction would lead to the production of the corresponding cation and the unstable radical (CF 3 ) 2 C−OH (in which the single electron would be delocalized onto the oxygen),25c diradical cations on the other hand would abstract hydride from the alkoxide and lead to two stable neutral species. Supporting this proposal is the fact that collidine was isolated as one of the products of the thermolysis, and that similar hydride ion abstractions by NH 2 + have been reported 26c…”