Experimental Measurement and Theory of Substituent Effects in π-Hydrogen Bonding: Complexes of Substituted Phenols with Benzene

2014 ◽  
Vol 79 (15) ◽  
pp. 6823-6831 ◽  
Author(s):  
Valia Nikolova ◽  
Sonia Ilieva ◽  
Boris Galabov ◽  
Henry F. Schaefer
Keyword(s):  
Hydrogen Bonding ◽  
Experimental Measurement ◽  
Substituent Effects ◽  
Substituted Phenols

Stabilities in the gas phase of the hydrogen bonded complexes, YC6H4OH-X−, of substituted phenols, YC6E4OH, with the halide anions X− (Cl−, Br−, I−)

1990 ◽  
Vol 68 (11) ◽  
pp. 2070-2077 ◽  
Author(s):  
Gary J. C. Paul ◽  
Paul Kebarle
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Proton Transfer ◽  
Gas Phase ◽  
Equilibrium Constants ◽  
Substituent Effects ◽  
Closed Shell ◽  
Bond Energies ◽  
Substituted Phenols ◽  
Hydrogen Bonded

The equilibria, YPhOH + Br− = YPhOH-Br−, involving 26 differently substituted phenols, were determined with a pulsed high pressure mass spectrometer. The −ΔG0 evaluated from the equilibrium constants represent the hydrogen bond free energies in YPhOH-Br−. These data and data for X− = Cl− and I−, determined previously in this laboratory, are used to examine the substituent effects on the hydrogen bonding. It was found that the hydrogen bond energies in YPhOH-X− increase approximately linearly with the gas phase acidities of the phenols, YPhOH. This is in agreement with earlier observations that showed the bond energies in AH-B−, where AH were oxygen and nitrogen acids and B− closed shell anions, increase with increasing acidity of AH.A detailed analysis of the substituent effects, which is possible for YPhOH-X−, shows that the relationship with the acidity of AH can be divided into two parts. One is the increasing extent of actual proton transfer from AH on formation of the hydrogen bonded complex. Such proton transfer occurs in YPhOH-X− only for the series X− = Cl−. The second effect, which occurs for Cl− and is dominant for Br− and I−, is not directly related to the acidity of the phenols (or AH in general) but depends on a similarity of the substituent effects on the acidity and the stabilization of YPhOH-X− (or AH-B− in general). The dominant contribution to YPhOH-X− stabilization in this case is due to the field effects of the substituents, i.e., π delocalization plays only a small part. Therefore, the correlation with the acidity of YPhOH, where π delocalization is important, is not very close. Keywords: hydrogen bonding, substituent effects, ion–molecule equilibria, stability constants, thermochemistry.

Substituent Effects on the Hydrogen Bonding between 4-Substituted Phenols and HF, H2O, NH3

2010 ◽  
Vol 21 (11) ◽  
pp. 1433-1439 ◽  
Author(s):  
Yu-Hui Cheng ◽  
Yao Fu ◽  
Lei Liu ◽  
Qing-Xiang Guo
Keyword(s):  
Hydrogen Bonding ◽  
Substituent Effects ◽  
Substituted Phenols

Beziehungen zwischen Rotationsisomerie, Wasserstoffbrücken-Bindung und Substituenteneffekten der organischen Chemie / Relations between Rotational Isomerism, Hydrogen Bonding, and Substituent Effects in Organic Chemistry

1972 ◽  
Vol 27 (6) ◽  
pp. 663-674 ◽  
Author(s):  
Gotthard H. Krause ◽  
Herbert Hoyer
Keyword(s):  
Hydrogen Bonding ◽  
Substituent Effects ◽  
Intramolecular Hydrogen Bonding ◽  
Rotational Isomerism ◽  
Proton Acceptor ◽  
Single Bond ◽  
Free Enthalpy ◽  
Acceptor Group ◽  
Intramolecular Hydrogen ◽  
Derivatives Of

The change of free enthalpy involved in intramolecular hydrogen bonding is smaller if the proton acceptor group can rotate round a single bond, as compared to proton acceptor groups which are fixed in a position optimal for hydrogen bonding. Also, the free enthalpy change is altered when the rotation of the proton acceptor is sterically restricted. This is demonstrated by comparing the absorptions of carbonyl stretching vibrations in the infrared spectra of certain compounds showing rotational isomerism. In the present study derivatives of 5-hydroxy-2,2-dimethyl-6-carbomethoxychromanone- (4), 3-nitrosalicylaldehyde and 3-nitro-2-hydroxy-acetophenones substituted in the position 5 and 6 are examined.

ChemInform Abstract: HYDROGEN BONDING INTERACTIONS OF ALIPHATIC AMINES WITH ORTHO-SUBSTITUTED PHENOLS

1980 ◽  
Vol 11 (1) ◽  
Author(s):  
L. FARAH ◽  
G. GILES ◽  
D. WILSON ◽  
A. OHNO ◽  
R. M. SCOTT
Keyword(s):  
Hydrogen Bonding ◽  
Aliphatic Amines ◽  
Substituted Phenols ◽  
Hydrogen Bonding Interactions

Hydrogen Bonding of Phenols or Their Radical Cations with Water or Ammonia:  Substituent Effects and the Influence on Phenol Oxidation

2002 ◽  
Vol 106 (47) ◽  
pp. 11518-11525 ◽  
Author(s):  
Yong Feng ◽  
Lei Liu ◽  
Ying Fang ◽  
Qing-Xiang Guo
Keyword(s):  
Hydrogen Bonding ◽  
Substituent Effects ◽  
Radical Cations ◽  
Phenol Oxidation

An NMR study of hydrogen-bonding in substituted phenols

1966 ◽  
Vol 21 (1-4) ◽  
pp. 302-309 ◽  
Author(s):  
V.S. Griffiths ◽  
G. Socrates
Keyword(s):  
Hydrogen Bonding ◽  
Substituted Phenols ◽  
Nmr Study

Substituent effects in XCCH⋯NH3 (or OH2, FH) hydrogen bonding

2001 ◽  
Vol 338 (1) ◽  
pp. 61-66 ◽  
Author(s):  
Rong Chen ◽  
Ke-Chun Zhang ◽  
Lei Liu ◽  
Xiao-Song Li ◽  
Qing-Xiang Guo
Keyword(s):  
Hydrogen Bonding ◽  
Substituent Effects
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