Effects of Substituent and Leaving Group on the Gas-Phase SN2 Reactions of Phenoxides with Halomethanes: A DFT Investigation

2009 ◽  
Vol 113 (38) ◽  
pp. 10359-10366 ◽  
Author(s):  
Qiang-gen Li ◽  
Ying Xue
Keyword(s):  
Gas Phase ◽  
Sn2 Reactions ◽  
Leaving Group

Neutral Metal Atoms Acting as a Leaving Group in Gas-Phase SN2 Reactions: M(CH3)++ NH3→ CH3NH3++ M (M = Zn, Cd, Hg)

2012 ◽  
Vol 31 (10) ◽  
pp. 3816-3824 ◽  
Author(s):  
Robert Kretschmer ◽  
Maria Schlangen ◽  
Martin Kaupp ◽  
Helmut Schwarz
Keyword(s):  
Gas Phase ◽  
Sn2 Reactions ◽  
Metal Atoms ◽  
Leaving Group ◽  
Neutral Metal

Effect of the Leaving Group on the Rates of SN2 and SN2' Reactions in Allylic Systems

1960 ◽  
Vol 82 (11) ◽  
pp. 2881-2888 ◽  
Author(s):  
F. G. Bordwell ◽  
Phillip E. Sokol ◽  
James D. Spainhour
Keyword(s):  
Sn2 Reactions ◽  
Leaving Group

Mechanisms of aromatic nucleophilic substitution by the ambident thiocyanate ion

1973 ◽  
Vol 26 (2) ◽  
pp. 273 ◽  
Author(s):  
DE Giles ◽  
AJ Parker
Keyword(s):  
Nucleophilic Substitution ◽  
Transition States ◽  
Reactivity Ratio ◽  
Substitution Reactions ◽  
Aromatic Nucleophilic Substitution ◽  
Thiocyanate Ion ◽  
Sn2 Reactions ◽  
Leaving Group ◽  
Electrophilic Reactivity ◽  
Saturated Carbon Atom

Sulphur/nitrogen reactivity ratios in a series of aromatic nucleophilic substitution reactions of ambident thiocyanate ion have been determined. There are profound differences from the pattern found in SN2 reactions at a saturated carbon atom. Abnormal transition states, involving interactions between entering and leaving group, are likely in the bond-breaking step of the intermediate complex in reactions of thiocyanate ion with 1-fluoro-2,4-dinitrobenzene and with 2,4- dinitrophenyl 4-toluenesulphonate. The nitro-substituted aryl thiocyanates are shown to be tri-functional electrophiles, with reactive centres at aromatic carbon, at cyanide carbon, and at sulphur. Aryl 4-toluenesulphonates are bifunctional electrophiles with reactive centres at aryl carbon and sulphonyl sulphur. The site of attack by nucleophiles depends on the nature of the nucleophile. The sulphur/nitrogen reactivity ratio of ambident SCN-, and the electrophilic reactivity of tri- and bi-functional substrates, are in most instances consistent with the Hard and Soft Acids and Bases principle. Exceptions to the principle in some instances reveal differences between the SNAr and SN2 mechanisms, and in others indicate abnormal transition states.

scholarly journals Benchmark ab Initio Energy Profiles for the Gas-Phase SN2 Reactions Y-+ CH3X → CH3Y + X-(X,Y = F,Cl,Br). Validation of Hybrid DFT Methods

2001 ◽  
Vol 105 (5) ◽  
pp. 895-904 ◽  
Author(s):  
Srinivasan Parthiban ◽  
Glênisson de Oliveira ◽  
Jan M. L. Martin
Keyword(s):  
Ab Initio ◽  
Gas Phase ◽  
Dft Methods ◽  
Sn2 Reactions ◽  
Energy Profiles

Photoinitiation of Gas-Phase SN2 Reactions through the Evans−Polanyi Excited State Surface

1997 ◽  
Vol 119 (21) ◽  
pp. 5067-5068 ◽  
Author(s):  
Caroline E. H. Dessent ◽  
Mark A. Johnson
Keyword(s):  
Excited State ◽  
Gas Phase ◽  
Sn2 Reactions

Gas-phase SN2 reactions at silicon and carbon centers. An experimental appraisal of theory

1976 ◽  
Vol 98 (4) ◽  
pp. 894-899 ◽  
Author(s):  
J. D. Payzant ◽  
K. Tanaka ◽  
L. D. Betowski ◽  
D. K. Bohme
Keyword(s):  
Gas Phase ◽  
Carbon Centers ◽  
Sn2 Reactions

Charge Distributions of Gas-phase SN2 Reactions: ABEEM-σπ Method Compared with Potential Acting on an Electron in a Molecule

2015 ◽  
Vol 44 (8) ◽  
pp. 1074-1076 ◽  
Author(s):  
Yanli Ding ◽  
Xiaojing Han ◽  
Changliang Sun ◽  
Jirong Mu
Keyword(s):  
Gas Phase ◽  
Sn2 Reactions ◽  
Charge Distributions

Intrinsic Structure-Reactivity Relationships in Gas-Phase SN2 Reactions: Identity Exchange of Substituted Benzyl Chlorides with Chloride Ion

1994 ◽  
Vol 116 (6) ◽  
pp. 2471-2480 ◽  
Author(s):  
Brian D. Wladkowski ◽  
James L. Wilbur ◽  
John I. Brauman
Keyword(s):  
Gas Phase ◽  
Chloride Ion ◽  
Intrinsic Structure ◽  
Sn2 Reactions ◽  
Benzyl Chlorides
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