Application of photoelectron spectroscopy to substituent effects. Conformational analysis of some flexible allylic ethers and alcohols

1979 ◽  
Vol 57 (14) ◽  
pp. 1890-1896 ◽  
Author(s):  
R. S. Brown ◽  
R. W. Marcinko ◽  
A. Tse
Keyword(s):  
Conformational Analysis ◽  
Gas Phase ◽  
Photoelectron Spectroscopy ◽  
Ionization Energy ◽  
Substituent Effects ◽  
Allylic Alcohol ◽  
Tert Butyl ◽  
Cis And Trans ◽  
Allylic Ethers

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.

Photoelectron spectroscopy, gas phase acidity, and thermochemistry of tert-butyl hydroperoxide: Mechanisms for the rearrangement of peroxyl radicals

1998 ◽  
Vol 109 (23) ◽  
pp. 10293-10310 ◽  
Author(s):  
Eileen P. Clifford ◽  
Paul G. Wenthold ◽  
Roustam Gareyev ◽  
W. Carl Lineberger ◽  
Charles H. DePuy ◽  
...  
Keyword(s):  
Gas Phase ◽  
Photoelectron Spectroscopy ◽  
Peroxyl Radicals ◽  
Butyl Hydroperoxide ◽  
Tert Butyl ◽  
Gas Phase Acidity ◽  
Tert Butyl Hydroperoxide

ChemInform Abstract: Substituent Effects in the Gas-Phase Thermolysis of Aryl tert.-Butyl Ethers and Sulfides

ChemInform ◽  
2010 ◽  
Vol 22 (4) ◽  
pp. no-no
Author(s):  
G. MARTIN ◽  
H. MARTINEZ ◽  
J. ASCANIO
Keyword(s):  
Gas Phase ◽  
Substituent Effects ◽  
Tert Butyl

scholarly journals The oxidation potentials of cis- and trans-1,2-diphenylcyclopropane and cis- and trans-2,3-diphenyloxirane

1979 ◽  
Vol 57 (16) ◽  
pp. 2098-2102 ◽  
Author(s):  
D. R. Arnold ◽  
P. C. Wong
Keyword(s):  
Gas Phase ◽  
Photoelectron Spectroscopy ◽  
Phenyl Group ◽  
Membered Ring ◽  
Empirical Correlation ◽  
Charge Transfer Complexes ◽  
Long Wavelength ◽  
Oxidation Potentials ◽  
Electron Withdrawal ◽  
Cis And Trans

The oxidation potentials of cis- and trans-1,2-diphenylcyclopropane (1) and cis- and trans-2,3-diphenyloxirane (2) have been determined by cyclic voltammetry, spectroscopically (using an empirical correlation of the long wavelength transition of the charge-transfer complexes with tetracyanoethylene) and by using an empirical correlation based upon the gas phase ionization potentials measured by photoelectron spectroscopy. The values obtained by these three very different techniques agree to within ±0.15 V. The results are interpreted in terms of the initial formation of the phenyl radical cation with the three-membered ring intact. The higher oxidation potentials of cis- and trans-2, relative to those of cis- and trans-1, are attributed to inductive electron withdrawal from the phenyl group by the oxygen of the oxirane ring. The relevance of these results to the photosensitized (electron transfer) behaviour of these compounds is discussed.

Gas Phase UPS Investigation of Trans-Azobenzenes

1979 ◽  
Vol 34 (12) ◽  
pp. 1496-1499 ◽  
Author(s):  
S. Millefiori ◽  
A. Millefiori ◽  
S. Pignataro ◽  
G. Distefano ◽  
F. P. Colonna
Keyword(s):  
Gas Phase ◽  
Electron Donor ◽  
Photoelectron Spectroscopy ◽  
Ionization Energy ◽  
Substituent Effect ◽  
Semiempirical Calculations ◽  
Occupied Orbital ◽  
Absorption Measurements

AbstractThe first two ionization energy values of p-substituted trans-azobenzenes pX-C6H4-N = N-C6H5 (X = NH2, OCH3, OH, CH3, H, Cl, COOH and NO2) are reported. These have been obtained by U.V. (HeI and HeII) photoelectron spectroscopy (UPS). The substituent effect indicates that for electron donor substituents, the highest occupied orbital is π-type. This is confirmed by semiempirical calculations. When the substituent is H or a withdrawing group, the first two bands heavily overlap, and in these cases no certain assignment was possible, in spite of the several approaches used. The UPS data are discussed along with previous polarographic and U.V. absorption measurements.

UPS Spectra of Cis and Trans 1-Phenyl-2-(4-Pyridyl) Cyclopropanes. A Comparison with Charge Transfer and Protonation Data

1979 ◽  
Vol 34 (2) ◽  
pp. 245-247
Author(s):  
G. Distefano ◽  
A. Modelli ◽  
V. Mancini
Keyword(s):  
Charge Transfer ◽  
Gas Phase ◽  
Ionization Energy ◽  
Energy Region ◽  
Experimental Error ◽  
Two Phases ◽  
Cis And Trans

AbstractThe low ionization energy region of the USP spectra of cis- and trans-1-(4-X-phenyl)-2-(4pyridyl) cyclopropanes is assigned by analogy with those of simple related molecules. Corresponding IE values of cis and trans derivatives are equal within the limits of experimental error. This finding indicates, at variance with solution results previously obtained, that in the gas phase there is no sizeable through- space interaction between the MO’s of the two cis-aryl groups. A possible explanation of the different conformations of the cis derivatives in the two phases is proposed

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