OPTICAL AND ESR SPECTROSCOPY OF MATRIX-ISOLATED ETHYLNITRENE
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Date
1987
Journal Title
Journal ISSN
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Publisher
Ohio State University
Abstract
The ethylnitrene radical $CH_{3}CH_{2}N$ has been produced by the interaction of gaseous ethylazide with metastable $N_{2}$ or Ar generated in a microwave discharge, and has been trapped in $N_{2}$ and Ar matrices at 10 K. The UV absorption spectrum in solid nitrogen consists of a series of eleven bands beginning at 335 nm with an average vibrational interval of $320 cm^{-1}$. Intensity alternations suggest that two different vibrations are excited in the transition, probably a C-C-N bend corresponding to the observed spacing and a C-N stretch with vibrational frequency near $650 cm^{-1}$. The ESR spectrum at 8300 G indicates that ethyloitrene has a triple ground state with zero-field splitting parameters D = $1.67 cm^{-1}$ and E = $0.0033 cm^{-1}$ in a nitrogen matrix. The hyperfine splittings differ slightly in the x and y lines and have the average values of 16.0 G for N and 30.6 G for the methylene H. The spectral features associated with ethylnitrene were not observed through direct photolysis of the parent ethylazide either during or after deposition. The new optical data confirms previous speculation and expands the assignment of the UV spectrum of ethylnitrene; the high D value indicated by the ESR signals lends support to the suggestion that earlier assignments of the ESR spectrum of methylnitrene, $CH3N$, are incorrect.
Description
$^{1}$ T. Franken, D. Perner and M. W. Bosnali, Z. Naturforsch. Teil A25, 151 (1970). $^{2}$ R. F. Ferrante, J. Chem. Phys. 86, 25 (1987).
Author Institution: Department of Chemistry, Wake Forest University; Department of Chemistry, University of North Carolina-Chapel Hill
Author Institution: Department of Chemistry, Wake Forest University; Department of Chemistry, University of North Carolina-Chapel Hill