Molecular structure of the nitrile ylide derived from 3-phenyl-2H-azirine in a nitrogen matrix
Nitrile ylides derived from 3-phenyl-2H-azirine and five of its isotope-labeled counterparts were generated photochemically in 12 K nitrogen matrices and examined by FTIR. A prominent 1926-cm/sup -1/ feature in the unlabeled ylide's spectrum undergoes a 66-cm/sup -1/ shift with /sup 15/N substitution, and this effect is interpreted as being consistent only with the asymmetric stretching fundamental of a linear /sup -/C=/sup +/N=C skeleton. The spectra of the /sup 13/C- and D-labeled nitrile ylides corroborate this conclusion and clarify spectral regions where Fermi multiplets and overlapping absorptions complicate the interpretation. The allene-like nitrile ylide C/sub s/ geometry is retained over the temperature range 12-82 K, which suggests that this geometry is also adopted in solution where ylides have been implicated as 1,3-dipolar reactive intermediates from the photolysis of 2H-azirines.
- Research Organization:
- Lawrence Berkeley Lab., CA
- OSTI ID:
- 7032752
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 90:23; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
400500 -- Photochemistry
ABSORPTION
AZO COMPOUNDS
CHEMICAL PREPARATION
CHEMICAL REACTIONS
DATA
DECOMPOSITION
DEUTERIUM COMPOUNDS
ELEMENTS
EXPERIMENTAL DATA
FOURIER TRANSFORM SPECTROMETERS
HYDROGEN COMPOUNDS
IMINES
INFORMATION
INFRARED SPECTRA
LABELLED COMPOUNDS
MATRIX ISOLATION
MEASURING INSTRUMENTS
MOLECULAR STRUCTURE
NITRILES
NITROGEN
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
REACTION INTERMEDIATES
SPECTRA
SPECTROMETERS
SPECTROSCOPY
SYNTHESIS
ULTRALOW TEMPERATURE