Theoretical study on the reaction mechanism of cyclopropenylidene with azacyclopropane: ring expansion process

Tan, Xiaojun; Ying, Jie‐Zheng; Wang, Fang; Li, Ping

doi:10.1007/s00706-014-1174-0

Cited by 4 publications

(2 citation statements)

References 36 publications

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“…Silacyclopropenylidene and cyclopropenylidene have similar reactivity for this insertion process with azirane. The former’s energy barrier (118.1 kJ mol −1 ) is lower than the latter (210.7 kJ mol −1 ), 37 which demonstrated that the silacyclopropenylidene has higher reactive activity than cyclopropenylidene.…”

Section: Resultsmentioning

confidence: 99%

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

Tan

Wang

et al. 2020

Progress in Reaction Kinetics and Mechanism

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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.

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Section: Resultsmentioning

confidence: 99%

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

Tan

Wang

et al. 2020

Progress in Reaction Kinetics and Mechanism

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“…The large dipole moment of 3.32 D for c-C 3 H 2 as reported by Brown et al (1987), resulting from its carbenic structure, makes it and its derivatives ripe for study and detection via rotational spectroscopy (Spezzano et al 2012). The high interstellar concentrations of c-C 3 H 2 make it a strong candidate for one of the chemical building blocks that form larger organic species (Tan et al 2014). The potential of c-C 3 H 2 is only increased by its unique chemical reactivity.…”

Section: Introductionmentioning

confidence: 99%

The Formation of Monosubstituted Cyclopropenylidene Derivatives in the Interstellar Medium via Neutral–Neutral Reaction Pathways

Flint

Fortenberry

2022

ApJ

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Five substituted cyclopropenylidene derivatives (c-C3HX, X=CN, OH, F, NH2), all currently undetected in the interstellar medium (ISM), are found herein to have mechanistically viable, gas-phase formation pathways through neutral–neutral additions of ·X onto c-C3H2. The detection and predicted formation mechanism of c-C3HC2H introduces a need for the chemistry of c-C3H2 and any possible derivatives to be more fully explored. Chemically accurate CCSD(T)-F12/cc-pVTZ-F12 calculations provide exothermicities of additions of various radical species to c-C3H2, alongside energies of submerged intermediates that are crossed to result in product formation. Of the novel reaction mechanisms proposed, the addition of the cyano radical is the most exothermic at -16.10 kcal mol−1. All five products are found to or are expected to have at least one means of associating barrierlessly to form a submerged intermediate, a requirement for the cold chemistry of the ISM. The energetically allowed additions arise as a result of the strong electrophilicity of the radical species as well as the product stability gained through substituent-ring conjugation.

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Carbenes and Nitrenes

Gras

Chassaing

2017

Organic Reaction Mechanisms · 2014

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Theoretical study on the reaction mechanism of cyclopropenylidene with azacyclopropane: ring expansion process

Cited by 4 publications

References 36 publications

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

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

The Formation of Monosubstituted Cyclopropenylidene Derivatives in the Interstellar Medium via Neutral–Neutral Reaction Pathways

Carbenes and Nitrenes

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