Ab Initio and Direct Dynamics Studies of the Reaction of Singlet Methylene with Acetylene and the Lifetime of the Cyclopropene Complex

2005 ◽  
Vol 109 (9) ◽  
pp. 1890-1896 ◽  
Author(s):  
Hua-Gen Yu ◽  
James T. Muckerman
Keyword(s):  
Ab Initio ◽  
Direct Dynamics ◽  
Singlet Methylene

Ab Initio Study of the Stability of the Ylide-like Intermediate Methyleneoxonium in the Reaction between Singlet Methylene and Water

1996 ◽  
Vol 118 (23) ◽  
pp. 5408-5411 ◽  
Author(s):  
Carlos Gonzalez ◽  
Albeiro Restrepo-Cossio ◽  
Manuel Márquez ◽  
Kenneth B. Wiberg
Keyword(s):  
Ab Initio ◽  
Ab Initio Study ◽  
The Stability ◽  
Singlet Methylene

Ab initio and direct dynamics study on the C2H3 + CH3CH2OH reaction

2015 ◽  
Vol 114 (2) ◽  
pp. 315-324 ◽  
Author(s):  
Chaoxu Chen ◽  
Jinou Song ◽  
Chonglin Song ◽  
Gang Lv ◽  
Zhijun Li
Keyword(s):  
Ab Initio ◽  
Direct Dynamics

Ab Initio Direct Dynamics Studies on the Reactions of H Atoms with CCl4and CHCl3

2002 ◽  
Vol 106 (51) ◽  
pp. 12292-12298 ◽  
Author(s):  
Li Sheng ◽  
Ze-Sheng Li ◽  
Jing-Yao Liu ◽  
Jing-Fa Xiao ◽  
Chia-Chung Sun
Keyword(s):  
Ab Initio ◽  
Direct Dynamics

Facile formation of azines from reactions of singlet methylene and dimethylcarbene with precursor diazirines: theoretical explorations

1999 ◽  
Vol 77 (5-6) ◽  
pp. 540-549 ◽  
Author(s):  
Gennady V Shustov ◽  
Michael TH Liu ◽  
K N Houk
Keyword(s):  
Density Functional Theory ◽  
Ab Initio ◽  
Ring Opening ◽  
Density Functional ◽  
Activation Barrier ◽  
Thermal Reaction ◽  
Orbital Theory ◽  
Functional Theory ◽  
Activation Barriers ◽  
Singlet Methylene

The reactions of the singlet methylene (1a) and dimethylcarbene (1b), with their diazirine precursors, diazirine (2a), and dimethyldiazirine (2b), have been studied theoretically using ab initio and density functional theory. The reaction has no activation barriers for the parent system (1a + 2a) and proceeds via a reactive complex and a transition state with a small negative enthalpy of activation Δ Hnot =298 = -1.1 kcal mol-1, ΔSnot =298 = -34.4 cal mol-1 K-1, ΔG°298 = 9.2 kcal mol-1) for the dimethyl derivatives (1b + 2b). The formation of N-methylene diazirinium ylides (3a,b) is exothermic by 64-80 kcal mol-1. The isomer, 1,3-diazabicyclo[1.1.0]butane (4a), is more stable (5-12 kcal mol-1) than isomer 3a, but can neither be formed by direct thermal reaction of 1a with 2a nor undergo the direct rearrangement into formaldazine (5a). The rearrangement of ylides 3a,b into azines 5a,b proceeds by conrotatory C3-N1 ring opening. The predicted activation barrier of ca. 15 kcal mol-1 for the ring opening in ylide 3b is in excellent agreement with experimental data. The formation of pyridinium ylides from carbenes and pyridine is also studied.Key words: diazirinium ylide, ab initio MO (molecular orbital) theory, density functional theory, pyridinium ylide, CIS (singles configuration interaction) transition energies.

Ab initio direct dynamics studies on the reactions of chlorine atom with CH3−nFnCH2OH (n = 1–3)

2007 ◽  
Vol 28 (16) ◽  
pp. 2517-2530 ◽  
Author(s):  
Ying Wang ◽  
Jing-Yao Liu ◽  
Ze-Sheng Li
Keyword(s):  
Ab Initio ◽  
Chlorine Atom ◽  
Direct Dynamics
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