A Theoretical Study of the Role of Carbenes in the Kinetics and Mechanism of the Reactions of Synthesis and Pyrolysis of Carbon Suboxide

摘要

The results of quantum-chemical calculations of the kinetics and mechanism of the gas-phase thermal reactions of synthesis and decomposition of carbon suboxide are presented. The role of carbenes in the individual elementary stages is considered. The energy parameters of these stages and structures of intermediates formed in them are determined. The calculations are performed using the Moller-Plesset MP2 perturbation theory and the Dunning aug-cc-pVDZ correlated basis set with allowance for the zero-point-vibration energy (ZPE). The possibility of the formation of oxygen-containing C4O and C5O carbenes, which are formed in the dissociation of vibrationally excited chain oxides, produced, in turn, in the recombination of the carbon suboxide decomposition products, is for the first time predicted.