Photoelectron spectroscopy of chloro-substituted phenylnitrene anions.
The 355 nm time-of-flight negative ion photoelectron spectra of (o-, m-, and p-chlorophenyl)nitrene radical anions are reported. Electron affinities are obtained from the photoelectron spectra, and are 1.79 +/- 0.05, 1.82 +/- 0.05, and 1.72 +/- 0.05 eV for the (o-, m-, and p-chlorophenyl)nitrenes, respectively. Singlet-triplet splittings are determined to be 14 +/- 2, 15 +/- 1, and 14 +/- 2 kcal/mol, respectively. The shapes of the photoelectron bands indicate resonance interactions in the singlet states for the ortho- and para-substituted isomers, which is attributed to quinoidal structures of the open-shell singlet states. Reanalysis of the photoelectron spectrum of phenylnitrene anion leads to a revised experimental singlet-triplet splitting of 14.8 kcal/mol in the unsubstituted phenylnitrene.
Wijeratne
Neloni R
NR
Department of Chemistry, Purdue University, West Lafayette, Indiana 47906, USA.
Da Fonte
Maria
M
Ronemus
Alan
A
Wyss
Phillip J
PJ
Tahmassebi
Daryoush
D
Wenthold
Paul G
PG