Sean Moran, H. Benton Ellis, et al.
JACS
Photoelectron spectroscopy has been used to measure the electron affinities of the isocyanomethyl radicals: EA(CH2NC) = 1.059 ± 0.024 eV and EA(CD2NC) = 1.070 ± 0.024 eV. A Franck-Condon analysis of our spectra suggests that the isocyanomethide anion (”CH2NC) is a pyramidal species and a localized ion. This ion is bent out of the plane by 56 ± 5° with an inversion barrier of 650 ± 50 cm-1. These structural conclusions are examined by a series of ab initio Hartree-Fock and Moller-Plesset perturbation calculations on both the isocyanomethyl radical and isocyanomethide ion. Using the gas-phase acidity of CH3NC, we obtain the following bond-dissociation energy: DH0298(H-CH2NC) = 84.8 ± 3.1 kcal/mol. These results are used to compute the isomerization energies for “CH2NC —>° CH2CN“ and CH2NC —* CH2CN. These values are compared to other isocyano/cyano isomerizations. © 1987, American Chemical Society. All rights reserved.
Sean Moran, H. Benton Ellis, et al.
JACS
J. Pacansky, B. Liu, et al.
Journal of Organic Chemistry
D.J. DeFrees, P.R. Bunker, et al.
Journal of Molecular Spectroscopy
D.J. DeFrees, A.D. McLean
Journal of Physical Chemistry