Importance of frontier orbital interactions in addition reaction of water to disilene

2001 ◽  
Vol 84 (2) ◽  
pp. 192-197 ◽  
Author(s):  
Masae Takahashi ◽  
Tamás Veszprémi ◽  
Mitsuo Kira
Keyword(s):  
Addition Reaction ◽  
Frontier Orbital ◽  
Orbital Interactions

Frontier orbital interactions of electron pushing and drawing substituents with ferrocenyl group

1997 ◽  
Vol 40 (3) ◽  
pp. 236-244 ◽  
Author(s):  
Yueshun Jiang ◽  
Xiangdong Chai ◽  
Wensheng Yang ◽  
Dong Zhang ◽  
Yunwei Cao ◽  
...  
Keyword(s):  
Frontier Orbital ◽  
Orbital Interactions ◽  
Ferrocenyl Group

scholarly journals A theoretical study of the mechanism of the addition reaction between carbene and azacyclopropane

2010 ◽  
Vol 75 (5) ◽  
pp. 649-657 ◽  
Author(s):  
Xiaojun Tan ◽  
Ping Li ◽  
Weihua Wang ◽  
Gengxiu Zheng ◽  
Qiufen Wang
Keyword(s):  
Potential Barrier ◽  
Energy Surface ◽  
Addition Reaction ◽  
Exothermic Reaction ◽  
Geometry Optimization ◽  
Vibrational Analysis ◽  
Basis Set ◽  
Stationary Points ◽  
Orbital Interactions ◽  
Moller Plesset

The mechanism of the addition reaction between carbene and azacyclopropane was investigated using the second-order Moller-Plesset perturbation theory (MP2). By using the 6-311+G* basis set, geometry optimization, vibrational analysis and the energy properties of the involved stationary points on the potential energy surface were calculated. From the surface energy profile, it can be predicted that there are two reaction mechanisms. The first one (1) is carbene attack at the N atom of azacyclopropane to form an intermediate, 1a (IM1a), which is a barrierfree exothermic reaction. Then, IM1a can isomerize to IM1b via a transition state 1a (TS1a), in which the potential barrier is 30.0 kJ/mol. Subsequently, IM1b isomerizes to a product (Pro1) via TS1b with a potential barrier of 39.3 kJ/mol. The other one (2) is carbene attack at the C atom of azacyclopropane, firstly to form IM2 via TS2a, the potential barrier is 35.4 kJ/mol. Then IM2 isomerizes to a product (Pro2) via TS2b with a potential barrier of 35.1 kJ/mol. Correspondingly, the reaction energy for the reaction (1) and (2) is -478.3 and -509.9 kJ/mol, respectively. Additionally, the orbital interactions are also discussed for the leading intermediate.

Cycloadditions of Nitrile Oxides to α,β-Unsaturated Aldehydes. Frontier Orbital Interactions and Secondary Orbital Interactions at Work in Determining Regiochemistry

Tetrahedron ◽  
2000 ◽  
Vol 56 (25) ◽  
pp. 4299-4309 ◽  
Author(s):  
Lucio Toma ◽  
Paolo Quadrelli ◽  
Giancarlo Perrini ◽  
Remo Gandolfi ◽  
Cristiana Di Valentin ◽  
...  
Keyword(s):  
Frontier Orbital ◽  
Orbital Interactions ◽  
Nitrile Oxides ◽  
Unsaturated Aldehydes

Frontier orbital interactions in the hetero Diels–Alder cycloaddition of diazadienes

2008 ◽  
Vol 86 (5) ◽  
pp. 384-394 ◽  
Author(s):  
Pratibha Sharma ◽  
Ashok Kumar ◽  
Vinita Sahu ◽  
Jitendra Singh
Keyword(s):  
Chemical Potential ◽  
Molecular Orbital Calculation ◽  
Diels Alder ◽  
Reaction Pathways ◽  
Electronic Charge ◽  
Chemical Hardness ◽  
Frontier Orbital ◽  
Electrophilicity Index ◽  
Reactivity Pattern ◽  
Orbital Interactions

This work deals with the molecular orbital calculation studies performed on different diazadienes to assess their reactivity pattern. The interaction of these diazadienes with various electron-poor and electron-rich dienophiles leads to the formation of diazines and tetrazines as the cycloadducts. The results from frontier orbital interactions were used to rationalize the reactivity and predictability of NDAC and IEDDAC reaction pathways. Correlation studies were also performed to predict reactivity sequence using a number of electronic descriptors, such as electrophilicity index (ω), chemical potential (µ), electronic charge ΔNmax, and chemical hardness η. Moreover, these studies exhibit good compatibility with experimental observations.Key words: AM1, MNDO, PM3, diazadienes, tetrazines, electrophilicity index, chemical potential.

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