Photoelectron spectroscopy of methyl, ethyl, isopropyl, and tert-butyl radicals. Implications for the thermochemistry and structures of the radicals and their corresponding carbonium ions

1979 ◽  
Vol 101 (15) ◽  
pp. 4067-4074 ◽  
Author(s):  
F. A. Houle ◽  
J. L. Beauchamp
1979 ◽  
Vol 57 (14) ◽  
pp. 1890-1896 ◽  
Author(s):  
R. S. Brown ◽  
R. W. Marcinko ◽  
A. Tse

He(I) photoelectron (pe) spectroscopy is applied to determine the preferred gas phase conformations of a limited number of flexible allylic ethers and alcohols. Based on earlier observations that the π-ionization energy is increased more when the allylic C—O bond is coplanar (with the π-system) than when it is perpendicular, the pe spectrum of cis and trans-4-tert-butyl-2-cyclohexanol and their corresponding ethers, and 5α-hydroxy(and methoxy)-10α-Δ3-octalin have been determined. The results indicate that when a coplanar arrangement of the allylic C—O bond can be attained, it is preferred, leading to a favored conformation of the allylic alcohol or ether.


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