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Stabilities of isomeric halonium ions C/sub 2/H/sub 4/X/sup +/ (X = Cl, Br) by photoionization mass spectrometry and ion cyclotron resonance spectroscopy. General considerations of the relative stabilities of cyclic and acyclic isomeric onium ions

Journal Article · · J. Am. Chem. Soc.; (United States)
DOI:https://doi.org/10.1021/ja00499a032· OSTI ID:6378092
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At least two noninterconverting structural isomers of the halonium ions C/sub 2/H/sub 4/X/sup +/ (X = Cl, Br) are shown to exist in the gas phase. Threshold measurements of their formation through halide loss in the photoionization and fragmentation of corresponding dihaloethanes yield enthalpies of formation for these species. For X = Cl, the cyclic halonium ion is 5.6 kcal/mol less stable than the acyclic species CH/sub 3/CHCl/sup +/. These stabilities are reversed for X = Br, with the cyclic isomer being more stable by 1.4 kcal/mol. In addition, relative stabilities of a larger class of onium ions are inferred from ion cyclotron resonance studies of exchange reactions between C/sub 2/H/sub 4/X/sup +/ and HY to give C/sub 2/H/sub 4/Y/sup +/ and HX (X,Y = Cl, Br, OH, SH, NH/sub 2/, PH/sub 2/). From the preferred direction of these processes, stability is inferred to increase in the order X = OH < Cl < Br < SH, PH/sub 2/ < NH/sub 2/ for the cyclic onium ions and X = Cl < Br < SH, PH/sub 2/ < OH < NH/sub 2/ for their acyclic isomers.
Research Organization:
California Inst. of Tech., Pasadena
OSTI ID:
6378092
Journal Information:
J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 101:5; ISSN JACSA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400104 -- Spectral Procedures-- (-1987)
400201* -- Chemical &amp; Physicochemical Properties
400301 -- Organic Chemistry-- Chemical &amp; Physicochemical Properties-- (-1987)
ALKANES
AMINES
BROMINATED ALIPHATIC HYDROCARBONS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
CHLORINATED ALIPHATIC HYDROCARBONS
COMPARATIVE EVALUATIONS
CYCLOALKANES
DATA
DATA COMPILATION
DATA FORMS
DECOMPOSITION
ELECTRON SPECTROSCOPY
ENTHALPY
EXPERIMENTAL DATA
FLUIDS
FRAGMENTATION
GASES
GRAPHS
HALOGENATED ALIPHATIC HYDROCARBONS
HYDROCARBONS
HYDROXY COMPOUNDS
INFORMATION
ION CYCLOTRON RESONANCE SPECTROSCOPY
ION SPECTROSCOPY
IONIZATION
ISOMERS
MASS SPECTRA
MEDIUM TEMPERATURE
NUMERICAL DATA
ORGANIC BROMINE COMPOUNDS
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PHASE STABILITY
PHOTOCHEMICAL REACTIONS
PHOTOELECTRON SPECTROSCOPY
PHOTOIONIZATION
PHOTOLYSIS
PHYSICAL PROPERTIES
QUANTITY RATIO
RADICALS
SPECTRA
SPECTROSCOPY
STABILITY
TABLES
TEMPERATURE DEPENDENCE
THERMODYNAMIC PROPERTIES
THERMODYNAMICS
THIOLS
TIME DEPENDENCE
YIELDS