Carbanion spectroscopy: /sup -/CH/sub 2/NC

Journal Article · Wed Sep 30 04:00:00 EDT 1987 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00254a019· OSTI ID:6091416

Moran, S; Ellis, Jr, H B; DeFrees, D J; McLean, A D; Paulson, S E; Ellison, G B

Photoelectron spectroscopy has been used to measure the electron affinities of the isocyanomethyl radicals: EA(CH/sub 2/NC) = 1.059 +/- 0.024 eV and EA(CD/sub 2/NC) = 1.070 +/- 0.024 eV. A Franck-Condon analysis of their spectra suggests that the isocyanomethide anion (/sup -/CH/sub 2/NC) is a pyramidal species and a localized ion. This ion is bent out of the plane by 56 +/- 5/sup 0/ with an inversion barrier of 650 +/- 50 cm/sup -1/. These structural conclusions are examined by a series of ab initio Hartree-Fock and Moeller-Plesset perturbation calculations on both the isocyanomethyl radical and isocyanomethide ion. Using the gas-phase acidity of CH/sub 3/NC, they obtain the following bond-dissociation energy: DH/sup 0//sub 298/(H-CH/sub 2/NC) = 84.8 +/- 3.1 kcal/mol. These results are used to compute the isomerization energies for /sup -/CH/sub 2/NC ..-->.. CH/sub 2/CN/sup -/ and CH/sub 2/NC ..-->.. CH/sub 2/CN. These values are compared to other isocyano/cyano isomerizations.

• Research Organization: Univ. of Colorado, Boulder
• DOE Contract Number: AC02-80ER10722
• OSTI ID: 6091416
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:20; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
AFFINITY
ANIONS
BINDING ENERGY
BOND ANGLE
BOND LENGTHS
CARBANIONS
CHARGED PARTICLES
DATA
DEUTERIUM COMPOUNDS
DIMENSIONS
ELECTRON SPECTROSCOPY
ENERGY
ENERGY RANGE
EV RANGE
EV RANGE 01-10
EXPERIMENTAL DATA
HARTREE-FOCK METHOD
HYDROGEN COMPOUNDS
INFORMATION
IONS
KINETIC ENERGY
LASERS
LENGTH
MOLECULAR STRUCTURE
NITROGEN COMPOUNDS
NORMAL-MODE ANALYSIS
NUMERICAL DATA
PERTURBATION THEORY
PHOTOELECTRON SPECTROSCOPY
PHYSICAL PROPERTIES
POTENTIALS
SPECTROSCOPY
THERMODYNAMIC PROPERTIES