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A solvent-catalyzed four-molecular two-path solvolysis mechanism of t-butyl chloride or bromide in water or alcohol derived by density functional theory calculation and confirmed by high-resolution electrospray ionization-mass spectrometry

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DFT calculations at the LC-wHPBE/6-311++G(d,p) level found that the solvolysis of t-butyl chloride or bromide in water or alcohol has two paths: a frontside path and a backside path. The frontside path is a three-step reaction. The first step is to remove a halogen anion and generate the carbocation (CH3)3C+, and it follows the Lewis collision theory and needs to overcome a barrier Ea. The carbocation is the first active intermediate in the solvolysis. The second step is that the carbocation and two solvent molecules (CH3)3C+  + 2R–OH (R = H or alkyl) to complete a spontaneous termolecular electrophilic addition AE3, in which the carbocation is the electrophile, and the product is an σ-complex that it is the second active intermediate in solvolysis. The third step is the generation of the product through a spontaneous termolecular proton transfer Tp3 of the σ-complex. The backside path is a two-step reaction. The first step is a termolecular nucleophilic substitution SN3 of (CH3)3C–Cl or –Br + 2R–OH, the substitution follows the transition state theory and has to overcome an activition barrier ∆E*. The product is the same σ complex as in the frontside path. The second step is the termolecular proton transfer Tp3 of the σ complex to generate the target product also. Thus the Tp3 is a shared step in the two paths. The two paths contain three termolecular reactions, and the last solvent molecule is a catalyst. Both paths are a four-molecular solvolysis processes involving one molecule of the alkyl halide and three solvent molecules, and are weakly or very weakly endothermic reactions. High-resolution ESI–MS confirmed the presence of the two paths and the two active intermediates. Based on the results, a solvent-catalyzed four-molecular two-path solvolysis mechanism of (CH3)3C–Cl or –Br in water or alcohol proposed.

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I am grateful to Professor Guoshi Wu, Institute of Physical Chemistry, Tsinghua University for his support in DFT calculation. Grateful to Doctor Xuewang Gao, Institute of Physics and Chemistry, Chinese Academy of Sciences for his support in high-resolution ESI–MS detection.

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Correspondence to Hongchang Shi.

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Shi, H. A solvent-catalyzed four-molecular two-path solvolysis mechanism of t-butyl chloride or bromide in water or alcohol derived by density functional theory calculation and confirmed by high-resolution electrospray ionization-mass spectrometry. Reac Kinet Mech Cat (2020).

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  • t-Butyl chloride or bromide
  • Termolecular reaction
  • Four-molecular solvolysis
  • Two paths
  • Carbocation
  • σ-complex; DFT calculation
  • ESI–MS