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A theoretical investigation on the mechanism and kinetics of the thermal isomerization of Trimethylsilylcyclopropane using CBS-QB3

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Abstract

The kinetics of the thermal isomerization of trimethylsilylcyclopropane in the temperature range of 689.5–751.1 K have been theoretically studied using Rice-Ramsperger-Kassel-Marcus (RRKM) theory and transition state theory (TST) in conjugation with CBS-QB3 calculations. Three possible reaction pathways are identified. Among them, the three-membered ring opening and hydrogen atom transfer to the carbon atom bonded to the SiMe3 group and formation of the allyltrimethylsilane is the main reaction. Our calculated kinetic rate constants appear to be in excellent agreement with the available experimental data. The results show that the most abundant product derived from Trimethylsilylcyclopropane will be the (Z)-1-propenyltrimethylsilane under thermodynamic control, while the most favorable process is isomerization reaction of that reactant into the allyltrimethylsilane from a kinetic viewpoint. The regioselectivity of the reaction decreases with decreasing pressures and increasing temperatures. In proportion to greater barrier heights, pressures P > 10−4 bar are in general enough for confirming saturation of the calculated rate coefficients compared with the high-pressure limit of the RRKM rates.

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Authors and Affiliations

  1. Chemistry Department, Tonekabon Branch, Islamic Azad University, Tonekabon, Iran

    Ahmad Reza Oliaey

  2. Young Researchers and Elite Club, East Tehran Branch, Islamic Azad University, Tehran, Iran

    Abolfazl Shiroudi

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  1. Ahmad Reza Oliaey
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Correspondence to Ahmad Reza Oliaey.

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Oliaey, A.R., Shiroudi, A. A theoretical investigation on the mechanism and kinetics of the thermal isomerization of Trimethylsilylcyclopropane using CBS-QB3. Reac Kinet Mech Cat 130, 55–74 (2020). https://doi.org/10.1007/s11144-020-01775-y

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