Quantum-chemical Investigation on the Potential Energy Surface of the Reaction of BH2+ with C2H2

Abstract

Abstract: The potential energy surface of the ion-molecular reaction of BH₂⁺ with C₂H₂ in gas-phase has been investigated theoretically by using the B3LYP/6-311G(d,p) and the high-level electron-correlation CCSD(T)/6-311G(2df,p) single-point levels. Four isomers H₂B⁺·C₂H₂(a), HBCHCH₂⁺(b), H₂BCCH₂⁺(c) and H₂·BHCCH⁺(d) are found, among which isomer (b) is the most stable both thermodynamically and kinetically while isomers (a), (c) and (d) are kinetically unstable. The mechanism for the reaction BH⁺-²⁺C₂H₂→HBCCH⁺⁺H₂ is discussed based on the potential energy surface. It is shown that BH₂⁺ may carry out an electrophilic addition towards C₂H₂ followed by multi-step H-shifts and final H₂-elimination to form product HBCCH⁺⁺H₂, the total reaction is barrier-free and largely exothermic. The calculated results presented in this paper may be helpful for understanding the chemical behavior of electron-deficient borohydride cations such as BH₂⁺.

Key words: Borohydride cation, Potential energy surface, Reaction mechanism

CLC Number:

O641

TrendMD:

QU Zheng-Wang, LI Ze-Sheng, DING Yi-Hong, SUN Chia-Chong . Quantum-chemical Investigation on the Potential Energy Surface of the Reaction of BH₂⁺ with C₂H₂[J]. Chem. J. Chinese Universities, 2001, 22(10): 1711.

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Quantum-chemical Investigation on the Potential Energy Surface of the Reaction of BH₂⁺ with C₂H₂

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