Theoretical Investigation on H-Abstraction Reactions of Silanes with H and CH3 Attacking: A Comparative Study with Alkane Counterparts

Qilong Fang; Yan Zhang; Jingxian Xia; Yuyang Li

doi:10.1021/acsomega.1c07031

Theoretical Investigation on H-Abstraction Reactions of Silanes with H and CH₃ Attacking: A Comparative Study with Alkane Counterparts

ACS Omega. 2022 Feb 2;7(6):5558-5569. doi: 10.1021/acsomega.1c07031. eCollection 2022 Feb 15.

Authors

Qilong Fang¹, Yan Zhang¹, Jingxian Xia¹, Yuyang Li¹

Affiliation

¹ Key Laboratory for Power Machinery and Engineering of MOE, School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai 200240, P. R. China.

Abstract

Silicon-based organic precursors are widely applied in the vapor-fed flame synthesis of monocrystalline silicon, silicon dioxide, and silicon nitride. Due to the lack of kinetic investigations on reactions of silicon-based organic precursors, rate constants were usually analogized to those of their hydrocarbon counterparts. Investigations on the similarities and differences between the two types of compounds become necessary. This work reports a comparative theoretical investigation on H-abstraction reactions with H and CH₃ attacking for silanes and their alkane counterparts, including silane and methane, disilane, methylsilane and ethane, dimethylsilane and propane, trimethylsilane and iso-butane, and tetramethylsilane and neo-pentane at the domain-based local pair natural orbital coupled cluster with perturbative triple excitations (DLPNO-CCSD(T))/cc-pVTZ//M06-2X/cc-pVTZ level. The rate constants were calculated using the conventional transition-state theory coupled with the asymmetric Eckart tunneling corrections over 600-2000 K. The calculated results show that dramatic discrepancies exist between H-abstraction from silicon sites in silanes and equivalent carbon sites in their alkane counterparts with H and CH₃ attacking. The H-abstraction reactions from the primary carbon sites in silanes have generally lower barrier energies than the similar reactions in their alkane counterparts, while those in methylsilane and dimethylsilane with H attacking are the only two with higher barrier energies. Electrostatic potential mapped molecular van der Waals surfaces were adopted to provide insight into the calculated trends in barrier energies. The H-abstraction reactions from silicon sites in silanes have much higher rate constants than those from equivalent carbon sites in their alkane counterparts, especially under low-temperature conditions, while the rate constants of H-abstraction reactions from primary carbon sites in silanes and their alkane counterparts show relatively strong analogy.