Nucleophilic substitution at oxygen: the reaction of phosphine and ammonia with ammonia oxide. An ab initio investigation

1990 ◽  
Vol 55 (3) ◽  
pp. 1016-1019 ◽  
Author(s):  
Steven M. Bachrach
Keyword(s):  
Ab Initio ◽  
Nucleophilic Substitution

STUDIES ON NUCLEOPHILIC SUBSTITUTION REACTIONS AT CARBON (SN2(C)) AND SILICON (SN2(Si)) IN TERMS OF AB INITIO, POTENTIAL, ACTING ON AN ELECTRON IN A MOLECULE AND MOLECULAR FACE THEORY

2009 ◽  
Vol 08 (supp01) ◽  
pp. 983-1001 ◽  
Author(s):  
YAN-LI DING ◽  
LI-DONG GONG ◽  
DONG-XIA ZHAO ◽  
MING-BO ZHANG ◽  
ZHONG-ZHI YANG
Keyword(s):  
Ab Initio ◽  
Nucleophilic Substitution ◽  
Gas Phase ◽  
Chemical Bond ◽  
Energy Transition ◽  
High Energy ◽  
Ab Initio Method ◽  
Substitution Reactions ◽  
Nucleophilic Substitution Reactions ◽  
High Energy Transition

The gas-phase identity bimolecular nucleophilic substitution reactions, Cl- + CH3 Cl → ClCH3 + Cl- and Cl- + SiH3Cl → ClSiH3 + Cl- , are investigated in terms of the ab initio method, potential acting on an electron in a molecule (PAEM) and molecular face (MF) theory. The computations have been performed at the CCSD(T)/aug-cc-pVTZ//MP2/6-311+G(3df,3pd) and CISD/aug-cc-pVDZ level. Based on the ab initio calculation, according to the PAEM theory, the strength of a chemical bond during forming or rupturing may be characterized by the D pb , which is a new physical quantity relating to the barrier height of the PAEM along a chemical bond. According to the MF theory, the interesting pictures of electron transfer and interpolarization effect between the reactants are clearly demonstrated to provide visualized spatial changing features of the MF for the title reactions along the IRC routes. The reason why [ Cl⋯CH3⋯Cl]- is a high-energy transition state is also analyzed in comparison with the stable low-energy intermediate [ Cl⋯SiH3⋯Cl]- .

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.

Ab initio and DFT benchmark study for nucleophilic substitution at carbon (SN2@C) and silicon (SN2@Si)

2005 ◽  
Vol 26 (14) ◽  
pp. 1497-1504 ◽  
Author(s):  
A. Patrícia Bento ◽  
Miquel Solà ◽  
F. Matthias Bickelhaupt
Keyword(s):  
Ab Initio ◽  
Nucleophilic Substitution ◽  
Benchmark Study ◽  
Ab Initio And Dft

Ab initio investigation on nucleophilic ring opening of 1,3,2-oxathiaphospholane: nucleophilic substitution at phosphorus coupled with pseudorotation

1996 ◽  
Vol 263 (5) ◽  
pp. 691-696 ◽  
Author(s):  
Tadafumi Uchimaru ◽  
Wojciech J. Stec ◽  
Seiji Tsuzuki ◽  
Takuji Hirose ◽  
Kazutoshi Tanabe ◽  
...  
Keyword(s):  
Ab Initio ◽  
Nucleophilic Substitution ◽  
Ring Opening ◽  
Nucleophilic Ring Opening
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