A theoretical study on the bimolecular hydrogen exchange aminonitrene → trans-diimide. Comparison with formaldehyde photochemistry

1981 ◽  
Vol 59 (21) ◽  
pp. 3044-3048 ◽  
Author(s):  
M. J. H. Kemper ◽  
H. M. Buck
Keyword(s):  
Ab Initio Calculations ◽  
Ab Initio ◽  
Hydrogen Exchange ◽  
Theoretical Study ◽  
Experimental Studies ◽  
Activation Energies ◽  
Stabilization Energy ◽  
The Other ◽  
Hydrogen Shift

Ab initio calculations on the rearrangement aminonitrene → trans-diimide are reported. It is shown that a bimolecular hydrogen exchange is much easier than a unimolecular 1,2 hydrogen shift: the reactions have activation energies of 4 and 94 kcal/mol, respectively. The hydrogen exchange starts from dimers which have a fairly large stabilization energy. Infrared and Raman frequencies of these dimers are calculated in order to facilitate experimental studies. Some striking similarities are indicated between diimide chemistry and the photochemistry of formaldehyde. It is shown that results from one field are transferable to the other one. From this, some new experiments are suggested.

How Does Nucleophilic Aromatic Substitution in Nitroarenes Really Proceed: General Mechanism

Synthesis ◽  
2017 ◽  
Vol 49 (15) ◽  
pp. 3247-3254 ◽  
Author(s):  
Mieczysław Mąkosza
Keyword(s):  
Ab Initio Calculations ◽  
Ab Initio ◽  
Nucleophilic Substitution ◽  
Experimental Studies ◽  
Secondary Reaction ◽  
Nucleophilic Aromatic Substitution ◽  
General Mechanism ◽  
Primary Process ◽  
Nucleophilic Substitution Of Hydrogen ◽  
Aromatic Substitution

On the basis of previously published experimental studies and ab initio calculations, a general corrected mechanism of nucleophilic aromatic substitution was formulated. It was shown that conventional nucleophilic substitution of halogens is a slow secondary reaction whereas nucleophilic substitution of hydrogen is the fast primary process. The general mechanism embraces both of these alternative and complementary reactions.

THEORETICAL STUDY OF HYDROGEN BONDED CLUSTERS OF AMMONIA AND FULMINIC ACID

2008 ◽  
Vol 07 (02) ◽  
pp. 277-286 ◽  
Author(s):  
ABEDIEN ZABARDASTI ◽  
SAEID AMANI ◽  
MARYAM SALEHNASSAJ ◽  
ALI H. KIANFARD
Keyword(s):  
Ab Initio ◽  
Density Functional Calculations ◽  
Cluster Size ◽  
Density Functional ◽  
Theoretical Study ◽  
Cooperative Effect ◽  
Stabilization Energy ◽  
Topological Parameters ◽  
Hydrogen Bonded

Ab initio and density functional calculations are used to analyze the interaction between a molecule of fulminic acid with one, two, three, and four molecules of ammonia along with a 2:2 complex at B3LYP/6-311++G(d, p) and MP2/6-311++G(d, p) computational levels. Cooperative effect (CE) in terms of stabilization energy of clusters is calculated and discussed as well. For the studied clusters, the CE is increased with increasing cluster size. Red shifts of H – C stretching frequency for complexes involving HCNO as H -donor are predicted. Atom in molecules is used to analyze the cooperative effect on topological parameters.

Structural Aspects of Cyclopropyl Homoconjugation: Experimental Studies and Ab Initio Calculations

1997 ◽  
Vol 1997 (7) ◽  
pp. 1429-1435 ◽  
Author(s):  
Thomas Haumann ◽  
Jordi Benet-Buchholz ◽  
Frank-Gerrit Klärner ◽  
Roland Boese
Keyword(s):  
Ab Initio Calculations ◽  
Ab Initio ◽  
Experimental Studies ◽  
Structural Aspects
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