Theoretical investigation on acetylene cyclotrimerization catalysed by TiO 2 and Ti

Abstract The reaction mechanisms for acetylene cyclotrimerization using TiO 2 and Ti catalysts were studied by the density functional theory (DFT) method. Interestingly, the reaction catalysed by TiO 2 occurs on the potential energy surface (PES) with a singlet state. For the same reaction catalysed...

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Bibliographic Details
Published in:Journal of physical organic chemistry 2019-05, Vol.32 (5)
Main Authors: Deng, Zhe‐Peng, Wang, Yong‐Cheng, Mou, Dan, Sun, Yu, Da, Hu, Gao, Jian‐De
Format: Article
Language:English
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Summary:Abstract The reaction mechanisms for acetylene cyclotrimerization using TiO 2 and Ti catalysts were studied by the density functional theory (DFT) method. Interestingly, the reaction catalysed by TiO 2 occurs on the potential energy surface (PES) with a singlet state. For the same reaction catalysed by Ti, spin‐orbit coupling (SOC) calculations were performed to discuss spin inversion between the triplet and singlet PESs. The chance that an electron hops in the vicinity of the minimum‐energy crossing point (MECP) was verified regarding the Landau‐Zener model. The possibilities of single ( ) and double ( ) at MECP1 (SOC = 253.38 cm −1 ) are about 0.35 and 0.46, respectively. The energetic span model developed by Kozuch was applied in the above reactions. The turnover frequency (TOF)‐determining transition state (TDTS) and TOF‐determining intermediate (TDI) were verified. The TOF value indicates that Ti is a more active catalyst compared with TiO 2 in C 2 H 2 cyclotrimerization.
ISSN:0894-3230
1099-1395
DOI:10.1002/poc.3934