Application of photoelectron spectroscopy to intramolecularly hydrogen-bonded systems. Part III. The photoelectron spectra of cis and trans 2-substituted cyclopentanols and cis and trans 2-substituted cyclohexanols

1976 ◽  
Vol 54 (12) ◽  
pp. 1929-1937 ◽  
Author(s):  
R. S. Brown
Keyword(s):  
Hydrogen Bonding ◽  
Photoelectron Spectroscopy ◽  
Intramolecular Hydrogen Bonding ◽  
Photoelectron Spectra ◽  
Molecular Orbital Calculations ◽  
Cis And Trans Isomers ◽  
Koopmans Theorem ◽  
Hydrogen Bonded Systems ◽  
Intramolecular Hydrogen ◽  
Cis And Trans

The photoelectron spectra of several well defined molecules exhibiting intramolecular hydrogen bonding has been determined and the analysis of the spectra is in accord with recent molecular orbital calculations of related systems. The experimentally determined enthalpies of the hydrogen bonds in cis-2-aminocyclopentanol and cis- and trans-2-aminocyclohexanol do not correlate in any simple fashion with the shifts in the ionization energies of the nO and nN orbitals compared to a model which precludes hydrogen bonding. The spectral differences attributed to hydrogen bonding in the cis and trans 2-substituted cyclanols cannot be attributed to differences in the through-bond interaction of the n orbitals on either atom since the cis and trans isomers of 1,2-dimethoxycyclopentane and 1,2-dimethoxycyclohexane show virtually identical pe spectra. A discussion of the applicability of Koopmans' theorem and the effect of the hydrogen bond in both the ion and ground states is presented.

Photoelectron studies on intramolecularly hydrogen-bonded systems. I. The photoelectron spectra of cis- and trans-2-aminocyclopentanol, and cis- and trans-2-(N,N-dimethylamino)cyclopentanol

1976 ◽  
Vol 54 (4) ◽  
pp. 642-646 ◽  
Author(s):  
R. S. Brown
Keyword(s):  
Hydrogen Bonding ◽  
Ionization Energy ◽  
Lone Pair ◽  
Intramolecular Hydrogen Bonding ◽  
Photoelectron Spectra ◽  
Hydrogen Bonded Systems ◽  
Intramolecular Hydrogen ◽  
Cis And Trans ◽  
Infrared Data ◽  
Hydrogen Bonded

The photoelectron spectra of cis- and trans-2-aminocyclopentanol and cis- and trans-2-(N,N,-dimethylamino)cyclopentanol have been recorded and interpreted. The cis isomers exhibit N lone pair ionizations at higher ionization energy, and O lone pair ionizations at lower ionization energy than their trans isomers.The results are most consistent with the existence and observation of intramolecular hydrogen-bonding in the cis isomers. Infrared data on these systems also show that the cis isomers exist in the intramolecularly hydrogen-bonded state.

β-Amino ketoximes: a study of basicity, hydrogen bonding and isomerism

1977 ◽  
Vol 30 (7) ◽  
pp. 1467 ◽  
Author(s):  
HK Powell ◽  
JM Russell
Keyword(s):  
Hydrogen Bonding ◽  
Intramolecular Hydrogen Bonding ◽  
Calorimetric Data ◽  
Amino Groups ◽  
Or Groups ◽  
Inductive Effects ◽  
Methylene Groups ◽  
Secondary Amino ◽  
Intramolecular Hydrogen ◽  
Cis And Trans

The protonation reactions of the diamine dioxime 4,4,9,9-tetramethyl- 5,8-diazadodecane-2,11-dione dioxime and its O-methyl and bis-O-methyl ethers have been studied at 25�, I 0.10 M NaCl. The (substituted) oxime groups cause a marked reduction in the basicity of the secondary amino groups. log K (potentiometric) and ΔH (calorimetric) data are interpreted in terms of inductive effects of the oxime group and possible intramolecular hydrogen bonding, N+-H...N(OR)=, pKa for methoxy-amine, NH2OMe, has been determined (4.62�0.01, I 0.10 M NaCl, 25�). ������ P.m.r. spectra are assigned for β-amino ketoximes having α- methyl and α-methylene groups cis and trans to =N-OR groups. Infrared spectra are reported.

Intramolecular Hydrogen Bonding of vic-Diols in Cyclic Systems. II.1OH...O and OH... π-Electron Bonding in cis- and trans-1,2-Diaryl-1,2-acenaphthenediols2

1959 ◽  
Vol 81 (24) ◽  
pp. 6472-6477 ◽  
Author(s):  
Emil J. Moriconi ◽  
William F. O'Connor ◽  
Lester P. Kuhn ◽  
Elizabeth A. Keneally ◽  
Frederick T. Wallenberger
Keyword(s):  
Hydrogen Bonding ◽  
Intramolecular Hydrogen Bonding ◽  
Cyclic Systems ◽  
Intramolecular Hydrogen ◽  
Cis And Trans ◽  
In Cis
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