Related Experiment Video
Updated: Jun 22, 2026

Preparation and Use of Carbonyl-decorated Carbenes in the Activation of White Phosphorus
Published on: October 3, 2014
Theoretical study of the C(3P) + trans-C4H8 reaction
Yan Li1, Hui-ling Liu, Xu-ri Huang
1State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, People's Republic of China.
Abstract:
The complex triplet potential energy surface for the reaction of ground-state carbon atom C((3)P) with trans-C(4)H(8) is theoretically investigated at the B3LYP/6-311G(d,p) and G3B3(single-point) levels. Various possible isomerization and dissociation pathways are probed. The initial association between C((3)P) and trans-C(4)H(8) is found to be the C((3)P) addition to the C=C bond of trans-C(4)H(8) to barrierlessly generate the three-membered cyclic isomer 1 CH(3)-cCHCCH-CH(3). Subsequently, 1 undergoes a ring-opening process to form the chainlike isomer 3a cis-trans-CH(3)CHCCHCH(3), which can either lead to P(6)((2)CH(3)CHCCCH(3) + (2)H) via the C-H bond cleavage or to P(7)((2)CH(3)CHCCH + (2)CH(3)) via C-C bond rupture. These two paths are the most favorable channels of the title reaction. Other channels leading to products P(1)((2)CH(3)-cCHCCH + (2)CH(3)), P(2)((2)CH(3)-cCHCC-CH(3) + (2)H), P(3)(trans-(2)CH(3)CHCH + (2)C(2)H(3)), P(4)(cis-(2)CH(3)CHCH + (2)C(2)H(3)), P(5)((3)CH(3)CH + (1)CH(3)CCH), P(8)(cis-(2)CH(3)CHCHCCH(2) + (2)H), P(9)(trans-(2)CH(3)CHCHCCH(2) + (2)H), P(10)((2)CH(3)CCCH(2) + (2)CH(3)), and P(11)((2)CH(3)CHCCHCH(2) + (2)H), however, are much less competitive due to either kinetic or thermodynamic factors. Because the intermediates and transition states involved in the C((3)P) + trans-C(4)H(8) reaction all lie below the reactant, the title reaction is expected to be rapid, as is consistent with the measured large rate constant. Our results may be helpful for future experimental investigation of the title reaction.
More Related Videos
13:09Utilization of Stop-flow Micro-tubing Reactors for the Development of Organic Transformations
Published on: January 4, 2018
11:44Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions
Published on: March 20, 2014
Related Concept Videos
Thermal and Photochemical Electrocyclic Reactions: Overview
Photochemical Electrocyclic Reactions: Stereochemistry
Selection Rules: Photochemical Activation
[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement
Thermal Electrocyclic Reactions: Stereochemistry
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
Woodward–Hoffmann Selection Rules and Microscopic Reversibility
Pericyclic Reactions: Introduction
Pericyclic reactions can be classified into three categories: electrocyclic reactions, cycloaddition reactions, and sigmatropic rearrangements. Electrocyclic reactions and sigmatropic rearrangements are...