scholarly journals Theoretical study on the reaction between phosphacyclopropenylidene and ethylene: An alternative approach to the formation of phosphorus-bearing heterocyclic compound

2020 ◽  
Vol 85 (9) ◽  
pp. 1175-1184
Author(s):  
Mengyao Wu ◽  
Yilin Wang ◽  
Xiaojun Tan ◽  
Jinsong Gu
Keyword(s):  
Reaction Mechanism ◽  
Heterocyclic Compound ◽  
Energy Surface ◽  
Theoretical Study ◽  
Stationary Points ◽  
Frontier Molecular Orbital ◽  
Orbital Theory ◽  
Tricyclic Compound ◽  
Alternative Approach ◽  
Electron Withdrawing Group

The reaction mechanism between phosphacyclopropenylidene and ethylene has been systematically investigated at the B3LYP/6-311++G(d,p) level of theory in order to better understand the reactivity of unsaturated cyclic phosphorus-bearing carbene. Geometry optimizations and vibrational analyses have been performed for the stationary points on the potential energy surface of the system. Calculations show that the spiro bicyclic intermediate could be produced through the cycloaddition process between phosphacyclopropenylidene and ethylene initially. The reaction mechanism is illustrated with the frontier molecular orbital theory. Introduction of electron-withdrawing group in phosphacyclopropenylidene will better facilitate the addition process. Through subsequent ring-expanding and hydrogen-migrating process, fuse-ring and allene compounds could be produced, respectively. Furthermore, it?s easy for spiro bicyclic intermediate and another ethylene to form a spiro tricyclic compound. This study is helps to understand the reactivity of phosphacyclopropenylidene, the evolution of phosphorus-bearing molecules in space, and to offer an alternative approach to the formation of phosphorus-bearing heterocyclic compound.

Insights into the reaction mechanism between phosphacyclopropenylidene and methyleneimine: A theoretical study

2020 ◽  
Vol 19 (3) ◽  
pp. 237-244
Author(s):  
Yilin Wang ◽  
Mengyao Wu ◽  
Xiaojun Tan ◽  
Jinsong Gu
Keyword(s):  
Reaction Mechanism ◽  
Energy Surface ◽  
Theoretical Study ◽  
Stationary Points ◽  
Frontier Molecular Orbital ◽  
Molecular Orbital Theory ◽  
Orbital Theory ◽  
Tricyclic Compound ◽  
Alternative Approach ◽  
Electron Withdrawing Group

The reaction mechanism between phosphacyclopropenylidene and methyleneimine has been systematically investigated at the M06–2X/6–311++G(d,p) level of theory in order to better understand the reactivity of unsaturated cyclic phosphorus-bearing carbene. Geometry optimizations and vibrational analyses have been conducted for the stationary points on the potential energy surface of the system. Calculations show that the spiro bicyclic intermediate could be produced through the cycloaddition process between phosphacyclopropenylidene and methyleneimine initially. The reaction mechanism is illustrated with frontier molecular orbital theory. Introduction of electron-withdrawing group in phosphacyclopropenylidene will better facilitate the addition process. Through subsequent ring-expanding and hydrogen-migrating process, fuse-ring and allene compounds could be produced, respectively. Furthermore, it’s easy for spiro bicyclic intermediate and another methyleneimine to form a spiro tricyclic compound. This study is helpful to understand the reactivity of phosphacyclopropenylidene, the evolution of phosphorus-bearing molecules in space, and to offer an alternative approach to the formation of phosphorus-bearing heterocyclic compound.

scholarly journals Theoretical study on the reaction between silacyclopropenylidene and three-membered heterocyclic compounds (azirane and oxirane): An alternative approach to the formation of heterocyclic silylene

2020 ◽  
Vol 45 ◽  
pp. 146867832090205
Author(s):  
Xiaojun Tan ◽  
Mengyao Wu ◽  
Yilin Wang ◽  
Guizhi Shi ◽  
Jinsong Gu
Keyword(s):  
Reaction Mechanism ◽  
Potential Energy ◽  
Potential Energy Surface ◽  
Heterocyclic Compounds ◽  
Energy Surface ◽  
Theoretical Study ◽  
Stationary Points ◽  
Dissociation Process ◽  
Alternative Approach ◽  
Insertion Process

The reaction mechanism between silacyclopropenylidene and three-membered heterocyclic compounds (azirane and oxirane) has been systematically investigated at the B3LYP/6-311+G* level of theory in order to better understand the reactivity of unsaturated cyclic silylene. Geometry optimizations and vibrational analyses have been conducted for the stationary points on the potential energy surface of the system. Calculations show that the Si-spiroheterocyclic intermediate and four-membered heterocyclic silylene compound could be produced through the insertion process and subsequent dissociation process between silacyclopropenylidene and three-membered heterocyclic compounds. For the insertion process, it is easier for silacyclopropenylidene to insert into C-N bond of azirane than into C-O bond of oxirane. This study is helpful to understand the reactivity of silacyclopropenylidene, the evolution of silicon-bearing molecules in space, and to offer an alternative approach to the formation of enlarged heterocyclic silylene compound.

THEORETICAL STUDY ON THE SELF-REACTION MECHANISM OF CH2ClO2 RADICALS

2009 ◽  
Vol 08 (01) ◽  
pp. 119-142 ◽  
Author(s):  
WEN-MEI WEI ◽  
REN-HUI ZHENG ◽  
YAN TIAN ◽  
ZHI-HONG GU ◽  
YONG-YAN XIE
Keyword(s):  
Reaction Mechanism ◽  
Potential Energy ◽  
Potential Energy Surface ◽  
Complex Potential ◽  
Energy Surface ◽  
Theoretical Study ◽  
Transition States ◽  
The Self ◽  
Stationary Points ◽  
Energy Barriers

The complex potential energy surface for the self-reaction of CH 2 ClO 2 radicals, including 12 intermediates, 33 interconversion transition states, and 21 major dissociation products, was theoretically probed at the CCSD(T)/cc-pVDZ//B3LYP/6-311G(2d,2p) level of theory. The geometries and relative energies for various stationary points were determined. Based on the calculated CCSD(T)/cc-pVDZ potential energy surface, the possible mechanism for the studied system was proposed. It is shown that the most feasible channels are those leading to 22 CH 2 ClO + 3 O 2, 2 CH 2 ClO + 2 HO 2 + CHClO , 2 CH 2 ClO + HCl + 2 CH(O)O 2, 2 CH 2 ClO + 3 O 2 + 2 Cl + CH 2 O , and p,s,o- CH 2 ClOOOCl + CH 2 O with the energy barriers of 5.6, 11.8, 12.4, 12.4, and 13.5 kcal/mol, respectively. Their mechanisms are that CH 2 ClO 2 and CH 2 ClO 2 form a tetroxide intermediate first, then the intermediate dissociates to yield the productions or through multi-steps reactions to produce the final products.

scholarly journals Ab initio study regarding the evaluation of the antioxidant character of cyanidin, delphinidin and malvidin

2012 ◽  
Vol 10 (1) ◽  
pp. 180-186 ◽  
Author(s):  
Raluca Pop ◽  
Mariana Ştefănut ◽  
Adina Căta ◽  
Cristian Tănasie ◽  
Mihai Medeleanu
Keyword(s):  
Ab Initio ◽  
Theoretical Study ◽  
Molecular Descriptors ◽  
Frontier Molecular Orbital ◽  
Hydroxyl Groups ◽  
Molecular Orbital Theory ◽  
Ab Initio Study ◽  
Wide Spread ◽  
Orbital Theory ◽  
Dissociation Enthalpy

AbstractA theoretical study regarding the evaluation of the antioxidant character of three of the most wide-spread anthocyanidins (cyanidin, delphinidin and malvidin) was carried out at ab initio level. Different parameters (bond dissociation enthalpy, ionization potential, proton affinity, and electron transfer enthalpy) were computed for each OH group of the compounds in order to predict their antioxidant capacity. Several molecular descriptors based on frontier molecular orbital theory (hardness, electrophilicity, frontier charge density) were also calculated, as well as the atomic charges corresponding to the O atoms of the hydroxyl groups.

THEORETICAL STUDY ON THE MECHANISM OF THE REACTION OF Ni(d10 1S) + H2 + CO2 → NiCO + H2O

2005 ◽  
Vol 04 (02) ◽  
pp. 449-459 ◽  
Author(s):  
SONG QIN ◽  
CHANGWEI HU ◽  
HUAQING YANG
Keyword(s):  
Reaction Mechanism ◽  
Potential Energy ◽  
Potential Energy Surface ◽  
Energy Barrier ◽  
Energy Surface ◽  
Theoretical Study ◽  
Bond Cleavage ◽  
Rate Determining Step ◽  
Singlet Potential Energy Surface ◽  
Mechanism Of The Reaction

The detailed singlet potential energy surface (PES) of the reaction of Ni ( d 10 1 S ) + H 2 + CO 2→ NiCO + H2O is investigated at the CCSD(T) /6-311+ G(2d,2p) // B3LYP /6-311+ G(2d,2p) levels in order to explore possible reaction mechanism of CO 2 hydrogenation on Ni center. The calculation predicts that the co-interacted H 2 involved C–O bond cleavage of CO 2 molecule is prior to the dissociation of adsorbed H 2 molecule, and the entire reaction is exothermic by 297.3 kJ/mol with an energy barrier of 137.7 kJ/mol. The rate-determining step (RDS) for the overall reaction is predicted to be the insertion of Ni into the C–O bond of the CO 2 moiety.

Theoretical Study of the 1CHBr + 3O2 Reaction

2011 ◽  
Vol 396-398 ◽  
pp. 2438-2442
Author(s):  
Cong Yun Shi ◽  
Zhi Gang Zhan ◽  
Xing Zhong Liu ◽  
Chang Mei Ke ◽  
Zao Sheng Lv
Keyword(s):  
Potential Energy ◽  
Potential Energy Surface ◽  
Energy Surface ◽  
Theoretical Study ◽  
Transition States ◽  
Stationary Points ◽  
Singlet Potential Energy Surface ◽  
Mechanism Of The Reaction

The mechanism of the reaction of the monobromocarbene (1CHBr) with3O2was studied theoretically at the B3LYP/6-311++G(d,p) level on the singlet potential energy surface (PES). All structures of the stationary points (reactants, intermediates, transition states and products) were optimized and their energies were obtained. Three product channels, P1(HCO + BrO), P2(CO2+ HBr) and P3(CO + HOBr), are found. P2(CO2+ HBr) is the most favorable one both kinetically and thermodynamically.

Theoretical study of the stereo-dynamics of the H + HeH+(v = 0, j = 0) → H2+ + He reaction

2010 ◽  
Vol 88 (12) ◽  
pp. 899-904 ◽  
Author(s):  
Juanjuan Lv ◽  
Xinguo Liu ◽  
Jingjuan Liang ◽  
Haizhu Sun
Keyword(s):  
Reaction Mechanism ◽  
Cross Sections ◽  
Collision Energy ◽  
Energy Surface ◽  
Theoretical Study ◽  
Classical Trajectory ◽  
Direct Reaction ◽  
Generalized Polarization ◽  
Product Molecule ◽  
Out Of Plane

Theoretical study of the stereo-dynamics of the reaction, H + HeH+ (v = 0,  j = 0) → H 2+  + He, have been performed with quasi-classical trajectory (QCT) method at different collision energies on a new ab initio potential energy surface. The distributions of P(θr), P(ϕr) and four generalized polarization-dependent differential cross-sections have been calculated. The results indicate that both the orientation and alignment of the rotational angular momentum are impacted by collision energies. With the collision energy increases, the rotation of the product molecule has a preference of changing from the “in-plane” reaction mechanism to the “out-of-plane” mechanism. Although the reaction is mainly dominated by the direct reaction mechanism, the indirect mechanism plays a role while the collision energy is very low.

scholarly journals Theoretical study of the reaction mechanism and kinetics of the phenyl + propargyl association

2020 ◽  
Vol 22 (13) ◽  
pp. 6868-6880 ◽  
Author(s):  
Alexander N. Morozov ◽  
Alexander M. Mebel
Keyword(s):  
Reaction Mechanism ◽  
Energy Surface ◽  
Theoretical Study ◽  
Recombination Reaction ◽  
Propargyl Radical ◽  
Dependent Rate ◽  
Mechanism And Kinetics ◽  
Temperature And Pressure ◽  
High Level ◽  
Kinetics Of

Potential energy surface for the phenyl + propargyl radical recombination reaction has been studied using high-level ab initio calculations and temperature- and pressure-dependent rate constants and product yields have been computed employing RRKM-ME.

Sign in / Sign up

Export Citation Format

Share Document