Singlet-triplet energy gaps in highly stabilized nitrenium ions: experimental and theoretical study of 1,3-dimethylbenzotriazolium Ion
The first experimental determination of a singlet-triplet energy gap (DeltaE(st)) for an organic nitrenium ion was made for 1, 3-dimethylbenzotriazolium ion 1. Laser flash photolysis was used to determine DeltaE(st) for this persistent nitrenium ion and a value of -66 +/- 3 kcal mol(-)(1) was obtained. DFT calculations show excellent agreement with the experiment.
McIlroy
S
Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742-2021, and Department of Chemistry and Supercomputer Institute University of Minnesota, Minneapolis, Minnesota 55455-0431, USA.
Cramer
CJ
Falvey
DE