Interaction of dichlorocarbene with imines

Kostikov, R. R.; Khlebnikov, Alexander F.; Bespalov, V. Ya.

doi:10.1002/poc.610060203

Cited by 20 publications

(12 citation statements)

References 3 publications

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“…It is well known that carbene plays an important role in organic chemistry, especially for the addition reaction with the C=C and C=O double bonds [1][2][3][4]. Therefore, the studies of carben have attracted more attentions theoretically and experimentally.…”

Section: Introductionmentioning

confidence: 99%

Insights into the reaction mechanism between propadienylidene and ethylene: a DFT study

Tan

Liu

et al. 2011

Struct Chem

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The reaction mechanism between propadienylidene and ethylene has been systematically investigated employing the B3LYP/6-311??G** and MP2/cc-pVTZ levels of theory to better understand the reactivity of propadienylidene with unsaturated hydrocarbons. Geometry optimization, vibrational analysis, and energy property for the involved stationary points on the potential energy surface have been calculated. Two important initial reaction complexes characterized by three-and four-membered ring structures have been located firstly. After that, three different products possessing three-, four-, and five-membered ring characters have been obtained through three reaction pathways. In the first reaction pathway, a threemembered ring alkyne compound has been obtained. As for the second reaction pathway, it is a diffusion-controlled reaction, resulting in the formation of the four-membered ring conjugated diene compound. A five-membered conjugated diene compound has been obtained in the third reaction pathway, which is the most stable product in the available products thermodynamically. On the other hand, the second reaction pathway is the most favorable reaction to proceed kinetically.

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Section: Introductionmentioning

confidence: 99%

Insights into the reaction mechanism between propadienylidene and ethylene: a DFT study

Tan

Liu

et al. 2011

Struct Chem

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“…Carbenes play an important role in organic chemistry, especially for the addition reaction between carbene and C=O double bond [1][2][3][4]. Therefore, they have attracted much attention not only from theoretical but also applied chemists.…”

Section: Introductionmentioning

confidence: 99%

A theoretical study on the mechanism of the addition reaction between carbene and epoxyethane

Tan

Zheng

et al. 2009

Struct Chem

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The mechanism of addition reaction between carbene and epoxyethane has been investigated employing the MP2 and B3LYP/6-311?G* levels of theory. Geometry optimization, vibrational analysis, and energy property for the involved stationary points on the potential energy surface have been calculated. Based on the calculated results at the MP2/6-311?G* level of theory, it can be predicted that there are two reaction mechanisms (1) and (2). In the first reaction carbene attacks the atom O of epoxyethane to form an intermediate 1a (IM1a), which is a barrier-free exothermic reaction. Then, IM1a can isomerize to IM1b via a transition state 1a (TS1a), where the potential barrier is 48.6 kJ/mol. Subsequently, IM1b isomerizes to a product epoxypropane (Pro1) via TS1b with a potential barrier of 14.2 kJ/mol. In the second carbene attacks the atom C of epoxyethane firstly to form IM2 via TS2a. Then IM2 isomerizes to a product allyl alcohol (Pro2) via TS2b with a potential barrier of 101.6 kJ/mol. Correspondingly, the reaction energies for the reactions (1) and (2) are -448.4 and -501.6 kJ/mol, respectively. Additionally, the orbital interactions are also discussed for the leading intermediate. The results based on the B3LYP/6-311?G* level of theory are paralleled to those on the MP2/6-311?G* level of theory. Furthermore, the halogen and methyl substituent effects of H 2 C: on the two reaction mechanisms have been investigated. The calculated results indicate that the introductions of halogen or methyl make the addition reaction difficult to proceed.

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“…The carbon of carbene is linked to two adjacent groups by covalent bonds and possesses two nonbonding electrons. It is well known that carbene plays an important role in organic chemistry, therefore, the studies of carbene have attracted more attentions theoretically and experimentally [1][2][3][4][5][6][7][8] . C 3 H 2 is a class of highly unsaturated carbenes, which are of great interest for the chemistry of carbon-rich gas-phase environments.…”

Section: Introductionmentioning

confidence: 99%

Quantum Mechanical Study of the Insertion Reaction Between Cyclopropenylidene With R-H (R=f, Oh, Nh2, Ch3)

Ying

Liu

Wang

et al. 2013

J. Chil. Chem. Soc.

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To further reveal the reactivity of cyclopropenylidene with R-H compounds, mechanisms of four reactions between cyclopropenylidene and R-H (R=F, OH, NH 2 , CH 3) have been systematically investigated employing the second-order Møller-Plesset perturbation theory (MP2) method. Geometry optimization, vibrational analysis, and energy property for the involved stationary points on the potential energy surface have been calculated. All the mechanisms of four reactions are identical to each other. Based on the calculated results, there are three steps (step a, b, and c) along the reaction between cyclopropenylidene and R-H. For the first step, cyclopropenylidene is inserted into R-H to form an three-membered ring intermediate. For the second step, the three-membered ring is opened to form a carbene intermediate. With regard to the third step, it is H-transfered processes, the ultimate product is alkyne.

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Interaction of dichlorocarbene with imines

Cited by 20 publications

References 3 publications

Insights into the reaction mechanism between propadienylidene and ethylene: a DFT study

Insights into the reaction mechanism between propadienylidene and ethylene: a DFT study

A theoretical study on the mechanism of the addition reaction between carbene and epoxyethane

Quantum Mechanical Study of the Insertion Reaction Between Cyclopropenylidene With R-H (R=f, Oh, Nh2, Ch3)

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