Theoretical Study of the Mechanism of the ¹CBr₂ + ³O₂ Reaction

Abstract:

A detailed theoretical study was done in order to clarify the reaction mechanisms of the singlet dibromocarbene (¹CBr₂) with ³O₂ on the singlet potential energy surface (PES). All the geometries of reactants, intermediates, transition states and products were obtained at the B3LYP/6-311++G(d,p) level. Intrinsic reaction coordinate (IRC) calculations at the same level were carried out to confirm the connections between transition states and intermediates. It is found that the initial adduct Br2COO (C_s) is formed via a barrierless association in the ¹CBr₂ + ³O₂ reaction, and then some isomerizations and breakages of bonds take place, generating P₁ (BrCO + BrO), P₂ (CO + Br₂O), P₃ (CO₂ + Br₂) and P₄ (CO₂ + 2Br). P₃ (CO₂ + Br₂) is the most competitive channel kinetically and thermodynamically. P₄ (CO₂ + 2Br) is the least favorable one kinetically.

• Periodical: Advanced Materials Research (Volumes 356-360)
• Pages: 31-34
• DOI: https://doi.org/10.4028/www.scientific.net/AMR.356-360.31
• Online since: October 2011
• Authors: Cong Yun Shi, Jiao Zhang, Xing Zhong Liu
• Keywords: Dibromocarbene, Oxygen, Reaction Mechanism, Theoretical Calculation

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