n–π Electron donor–acceptor complexes. II. Aliphatic amines with dinitrobenzenes

1985 ◽  
Vol 63 (4) ◽  
pp. 903-907 ◽  
Author(s):  
Joaquín O. Singh ◽  
Jorge D. Anunziata ◽  
Juana J. Silber
Keyword(s):  
Electron Donor ◽  
Iterative Procedure ◽  
Steric Effect ◽  
Aliphatic Amines ◽  
Primary Amines ◽  
Substitution Reactions ◽  
Aromatic Nucleophilic Substitution ◽  
Donor Acceptor ◽  
Eda Complex ◽  
The Stability

The interaction of several aliphatic amines as n-donors and dinitrobenzenes (DNB) as π-acceptors has been studied in n-hexane. The formation of electron donor – acceptor (EDA) complexes is proposed to explain the spectroscopic behaviour of the mixtures. The stability constants (Ks) for these complexes have been calculated by an iterative procedure. For a given acceptor, the donor strength of RNH2 > R2NH > R3N was found. This order is explained by considering the role that steric effect may play in the EDA complex formation. On the other hand, the fact that for a given donor Ks follows the order 1,2-DNB > 1,3-DNB > 1,4-DNB, and that 1,2-DNB reacts with primary amines, led to the proposal of orientational complexes. These EDA complexes may be considered intermediates in aromatic nucleophilic substitution reactions.

n-π Electron donor–acceptor complexes. III. Aliphatic amines with dicyanobenzenes. Electric and steric effects of the N-substituents on complex formation

1986 ◽  
Vol 64 (8) ◽  
pp. 1491-1495 ◽  
Author(s):  
Jorge D. Anunziata ◽  
Norma S. Galaverna ◽  
Joaquín O. Singh ◽  
Juana J. Silber
Keyword(s):  
Electron Donor ◽  
Aliphatic Amines ◽  
Steric Effects ◽  
Probable Structure ◽  
Spectroscopic Behaviour ◽  
Amine Structure ◽  
Donor Acceptor ◽  
Substituent Constants ◽  
The Stability ◽  
Electronic And Steric Effects

The interaction of several aliphatic amines as n-donors with 1,2-, 1,3-, and 1,4-dicyanobenzenes as π acceptors in n-hexane has been studied. The spectroscopic behaviour of the mixtures leads us to propose that Electron Donor – Acceptor (EDA) complexes are formed. Correlations of the experimental data with the amine structure were performed for the amine–1,4-dicyanobenzene complexes. By means of free energy related substituents and regression analysis, the electronic and steric effects of three N-substituents were quantitatively separated. Thus, with K representing the stability constants of the complexes, the values of log K are correlated with Taft's polar substituent constants, σ*, and Hancock's corrected steric substituent constants, [Formula: see text] The results allowed the proposal of a probable structure of the complex, at least with respect to the donor orientation.

Electron donor-acceptor (EDA)-complex enabled SF5Cl addition on alkenes and alkynes

2021 ◽  
Vol 243 ◽  
pp. 109734
Author(s):  
Audrey Gilbert ◽  
Mélodie Birepinte ◽  
Jean-François Paquin
Keyword(s):  
Electron Donor ◽  
Donor Acceptor ◽  
Eda Complex

New Nitrogen-Rich Tripodal Molecules Based on Bis(pyrazol-1-ylmethyl)amines with Substituents Modulating Steric Hindrances and Electron Density of Donor Sites

2005 ◽  
Vol 70 (1) ◽  
pp. 34-40 ◽  
Author(s):  
Stefania Garbacia ◽  
Caroline Hillairet ◽  
Rachid Touzani ◽  
Olivier Lavastre
Keyword(s):  
Nmr Spectroscopy ◽  
Electron Density ◽  
Electron Donor ◽  
Primary Amines ◽  
Effect Of Substituents ◽  
H Nmr ◽  
Donor Acceptor ◽  
One Step ◽  
Steric Hindrances

Eight new substituted bis(pyrazol-1-ylmethyl)amines have been prepared in one step condensation of 1-(hydroxymethyl)-3,5-disubstituted pyrazoles with a series of primary amines. The effect of substituents of divers bulkiness and electron donor/acceptor power that have been introduced to these tridentate molecules is visualised by 1H NMR spectroscopy.

Sign in / Sign up

Export Citation Format

Share Document