scholarly journals Theoretical Study of the H-+CH3Cl SN2 Reaction

1979 ◽  
Vol 32 (10) ◽  
pp. 2289 ◽  
Author(s):  
ER Talaty ◽  
JJ Woods ◽  
G Simons
Keyword(s):  
Ab Initio ◽  
Theoretical Study ◽  
Reaction Path ◽  
Planar Structure ◽  
Sn2 Reaction ◽  
Leaving Group ◽  
Leaving Groups

A theoretical study of the C3v reaction path of the H- + CH3Cl → CH4+Cl- SN2 reaction with the use of the GAUSSIAN 70 program reveals an earlier departure of the leaving group than in other ab initio studies of similar reactions involving poorer leaving groups, and predicts an intermediate planar structure that is highly ionic and which should be represented as a tight ion triplet, H-[CH3+]Cl-.

DENSITY FUNCTIONAL STUDY OF SELECTED MONO-ZINC AND GEM-DIZINC RADICAL CARBENOID CYCLOPROPANATION REACTIONS: OBSERVATION OF AN EFFICIENT RADICAL ZINC CARBENOID CYCLOPROPANATION REACTION AND THE INFLUENCE OF THE LEAVING GROUP ON RING CLOSURE

2003 ◽  
Vol 02 (03) ◽  
pp. 357-369 ◽  
Author(s):  
CUNYUAN ZHAO ◽  
DONG-QI WANG ◽  
DAVID LEE PHILLIPS
Keyword(s):  
Density Functional ◽  
Theoretical Study ◽  
Radical Reaction ◽  
Ring Closure ◽  
Functional Study ◽  
Reaction Step ◽  
Leaving Group ◽  
Reaction Barriers ◽  
Leaving Groups ◽  
Zinc Carbenoid

We report a theoretical study of the cyclopropanation reactions of EtZnCHI, (EtZn)2CH EtZnCHZnI, and EtZnCIZnI radicals with ethylene. The mono-zinc and gem-dizinc radical carbenoids can undergo cyclopropanation reactions with ethylene via a two-step reaction mechanism similar to that previously reported for the CH2I and IZnCH2 radicals. The barrier for the second reaction step (ring closure) was found to be highly dependent on the leaving group of the cyclopropanation reaction. In some cases, the (di)zinc carbenoid radical undergoes cyclopropanation via a low barrier of about 5–7 kcal/mol on the second reaction step and this is lower than the CH2I radical reaction which has a barrier of about 13.5 kcal/mol for the second reaction step. Our results suggest that in some cases, zinc radical carbenoid species have cyclopropanation reaction barriers that can be competitive with their related molecular Simmons-Smith carbenoid species reactions and produce somewhat different cyclopropanated products and leaving groups.

Studies of the borderline between stepwise and concerted mechanisms of elimination: leaving group effects in elimination of (fluoren-9-ylmethyl)-ammonium ions

1983 ◽  
Vol 36 (9) ◽  
pp. 1831 ◽  
Author(s):  
F Larkin ◽  
RAM O'Ferrall
Keyword(s):  
Proton Transfer ◽  
Sodium Methoxide ◽  
Reaction Path ◽  
Intramolecular Proton Transfer ◽  
Ammonium Ions ◽  
Enhancing Effect ◽  
Leaving Group ◽  
Substituent Constants ◽  
Leaving Groups ◽  
Intermediate Rate

By comparison with related substrates β-elimination of (fluoren-9-ylmethyl)trimethylammonium ion to form dibenzofulvene in methanolic sodium methoxide is unexpectedly rapid. The reaction has been investigated as a possible example of an E2 mechanism at the borderline between concerted and stepwise reaction paths. Evidence from buffer saturation in dimethylaminoacetonitrile buffers and comparisons with other amine leaving groups suggests, however, that the mechanism is probably ElcB, with ionization to a carbanion intermediate rate-determining. As measured by σ* for the trimethylammonium group the rate of elimination is 105 times faster than predicted from a Taft correlation of rates of carbanion formation. Probably this reflects the sensitivity of substituent constants for monopoles to solvent and reaction, and a rate-enhancing effect from N-methylation of (fluoren-9-ylmethy1)amine. Comparison of the trimethylammonium leaving group with eliminations of neutral amines also confirms an earlier conclusion that intramolecular proton transfer is not an important reaction path in eliminations of amines activated by a β-fluorenyl group.

Theoretical study of the CH4+F→CH3+FH reaction. I. Ab initio reaction path

1996 ◽  
Vol 105 (8) ◽  
pp. 3152-3159 ◽  
Author(s):  
J. C. Corchado ◽  
J. Espinosa‐García
Keyword(s):  
Ab Initio ◽  
Theoretical Study ◽  
Reaction Path

The effect of steric size of leaving group on rates of the competing syn- and anti-pathways in biomolecular elimination

1980 ◽  
Vol 45 (8) ◽  
pp. 2171-2178
Author(s):  
Jiří Závada ◽  
Magdalena Pánková
Keyword(s):  
Comparative Analysis ◽  
Homologous Series ◽  
Leaving Group ◽  
Leaving Groups

Approximate rates of the competing syn- and anti-pathways have been determined in t-C4H9OK-t-C4H9OH promoted elimination from two homologous series of tosylates: I-OTs trans-III (R = H, CH3, C2H5, n-C3H7, i-C3H7, t-C4H9) and II-OTs trans-IV (R = CH3, C2H5, n-C3H7, i-C3H7, t-C4H9). A comparison has been made with rates of the same processes in the (+) elimination of the corresponding trimethylammonium salts I-N(CH3)3 trans-III and (+) II-N(CH3)3 trans-IV. The title effect is demonstrated by a comparative analysis of the rate patterns obtained for the two leaving groups.

Copper(II) complexes with tridentate halogen‐substituted Schiff base ligands: synthesis, crystal structures and investigating the effect of halogenation, leaving group and ligand flexibility on antiproliferative activities

2021 ◽  
Author(s):  
Nazanin Kordestani ◽  
Hadi Amiri Rudbari ◽  
Alexandra R Fernandes ◽  
Luís R Raposo ◽  
André Luz ◽  
...  
Keyword(s):  
Schiff Base ◽  
Anticancer Activity ◽  
Crystal Structures ◽  
Copper Complexes ◽  
Schiff Base Ligands ◽  
Leaving Group ◽  
Leaving Groups ◽  
Tridentate Schiff Base ◽  
Antiproliferative Activities

To investigate the effect of different halogen substituents, leaving groups and the flexibility of ligand on the anticancer activity of copper complexes, sixteen copper(II) complexes with eight different tridentate Schiff-base...

scholarly journals Concurrent Phenomena at the Reaction Path of the SN2 Reaction CH3Cl + F−. Information Planes and Statistical Complexity Analysis

Entropy ◽  
2013 ◽  
Vol 15 (12) ◽  
pp. 4084-4104 ◽  
Author(s):  
Moyocoyani Molina-Espíritu ◽  
Rodolfo Esquivel ◽  
Juan Angulo ◽  
Jesús Dehesa
Keyword(s):  
Complexity Analysis ◽  
Reaction Path ◽  
Statistical Complexity ◽  
Sn2 Reaction
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