Quantum Chemical and Kinetic Study on Radical/Molecule Formation Mechanism of Pre-Intermediates for PCTA/PT/DT/DFs from 2-Chlorothiophenol and 2-Chlorophenol Precursors
Abstract
:1. Introduction
2. Results
2.1. Formation of Radical Species C(T)PR1, C(T)PR2, C(T)PDR, (T)PR2, and (T)PDR from 2-CTP and 2-CP Molecules
2.2. Formation of Pre-Intermediates of PCTA/PT/DT/DFs via Radical/Molecule Coupling Reactions
2.2.1. Coupling Reaction of C(T)PR1 with 2-C(T)P
2.2.2. Coupling Reactions of C(T)PR2 and (T)PR2 with 2-C(T)P
2.2.3. Coupling Reactions of C(T)PDR and (T)PDR with 2-C(T)P
2.3. Rate Constant Calculations
3. Discussion
3.1. Formation of Radical Species C(T)PR1, C(T)PR2, C(T)PDR, (T)PR2, and (T)PDR from 2-CTP and 2-CP Molecules
3.2. Formation of Pre-Intermediates of PCTA/PT/DT/DFs via Radical/Molecule Coupling Reactions
3.2.1. Coupling Reaction of C(T)PR1 with 2-C(T)P
3.2.2. Coupling Reactions of C(T)PR2 and (T)PR2 with 2-C(T)P
3.2.3. Coupling Reactions of C(T)PDR and (T)PDR with 2-C(T)P
3.2.4. Comparing the Reactions of Thiophenoxy Radicals with 2-C(T)P Couplings, Sulfydryl/Hydroxyl-Substituted Phenyl Radicals with 2-C(T)P Couplings, and (thio)phenoxyl Diradicals with 2-C(T)P Couplings
3.3. Rate Constant Calculations
4. Materials and Methods
4.1. Density Functional Theory
4.2. Kinetic Calculation
4.3. Accuracy Verification
5. Conclusions
Supplementary Materials
Author Contributions
Funding
Conflicts of Interest
Abbreviations
PCDTs | polychlorinated dibenzothiophenes |
PCPTs | polychlorinated phenoxathiins |
PCTAs | polychlorinated thianthrenes |
PCDDs | polychlorinated dibenzo-p-dioxins |
PCDFs | polychlorinated dibenzofurans |
2-CP | 2-chlorophenol |
2-CTP | 2-chlorothiophenol |
CPR1 | 2-chlorophenoxy |
CPR2 | 2-hydroxyl-3-chloro-phenyl |
CPDR | chlorinated phenoxyl diradical |
PR2 | 2-hydroxylphenyl radical |
PDR | phenoxyl diradical |
CTPR1 | 2-chlorothiophenoxy |
CTPR2 | 2-sulfydryl-3-chloro-phenyl |
CTPDR | chlorinated thiophenoxyl diradical |
TPR2 | 2-sulfydrylphenyl radical |
TPDR | thiophenoxyl diradical |
TST | transition state theory |
IRC | intrinsic reaction coordinate |
KiSThelP | kinetic and statistical thermodynamic |
ZPE | zero-point energy |
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Reactions Arrhenius Formulas | Arrhenius Formulas |
---|---|
CPR1 + 2-CTP → IM1 via TS29 | k(T) = (2.09 × 10−15) exp (−11163/T) |
CPR1 + 2-CTP → IM2 + Cl via TS30 | k(T) = (1.79 × 10−15) exp (−12526/T) |
CPR1 + 2-CTP → IM3 via TS31 | k(T) = (1.43 × 10−15) exp (−17118/T) |
CPR1 + 2-CTP → IM4 + Cl via TS32 | k(T) = (3.90 × 10−15) exp (−15840/T) |
CPR1 + 2-CTP → IM5 via TS33 | k(T) = (1.42 × 10−15) exp (−17613/T) |
CPR1 + 2-CTP → IM6 + Cl TS34 | k(T) = (1.21 × 10−16) exp (−19231/T) |
CTPR1 + 2-CTP → IM7 via TS35 | k(T) = (2.37 × 10−15) exp (−2233/T) |
CTPR1 + 2-CTP → IM8 via TS36 | k(T) = (1.22 × 10−15) exp (−4093/T) |
CTPR1 + 2-CTP → IM9 via TS37 | k(T) = (1.40 × 10−15) exp (−19723/T) |
CTPR1 + 2-CTP → IM10 via TS38 | k(T) = (5.33 × 10−15) exp (−18080/T) |
CTPR1 + 2-CTP → IM11 via TS39 | k(T) = (1.99 × 10−15) exp (−19993/T) |
CTPR1 + 2-CTP → IM12 + Cl TS40 | k(T) = (5.24 × 10−16) exp (−22527/T) |
CTPR1 + 2-CP → IM13 via TS41 | k(T) = (1.14 × 10−14) exp (−2790/T) |
CTPR1 + 2-CP → IM14 + Cl via TS42 | k(T) = (1.01 × 10−14) exp (−4524/T) |
CTPR1 + 2-CP → IM15 via TS43 | k(T) = (6.13 × 10−15) exp (−19327/T) |
CTPR1 + 2-CP → IM16 + Cl via TS44 | k(T) = (1.06 × 10−14) exp (−17908/T) |
CTPR1 + 2-CP → IM17 via TS45 | k(T) = (4.46 × 10−15) exp (−19296/T) |
CTPR1 + 2-CP → IM18 + Cl TS46 | k(T) = (1.29 × 10−15) exp (−21760/T) |
CPR2 + 2-CTP → IM19 via TS47 | k(T) = (1.42 × 10−14) exp (−3082/T) |
CPR2 + 2-CTP → IM20 + Cl via TS48 | k(T) = (3.37 × 10−15) exp (−6141/T) |
CTPR2 + 2-CTP → IM21 via TS49 | k(T) = (7.46 × 10−15) exp (−3994/T) |
CTPR2 + 2-CTP → IM22 + Cl via TS50 | k(T) = (1.20 × 10−15) exp (−7520/T) |
CTPR2 + 2-CP → IM23 via TS51 | k(T) = (3.19 × 10−14) exp (−4022/T) |
CTPR2 + 2-CP → IM24 + Cl TS52 | k(T) = (5.48 × 10−15) exp (−6518/T) |
PR2 + 2-CTP → IM25 via TS53 | k(T) = (1.26 × 10−14) exp (−3668/T) |
PR2 + 2-CTP → IM26 + Cl via TS54 | k(T) = (1.53 × 10−15) exp (−5987/T) |
TPR2 + 2-CTP → IM27 via TS55 | k(T) = (1.21 × 10−14) exp (−4148/T) |
TPR2 + 2-CTP → IM28 + Cl via TS56 | k(T) = (1.21 × 10−15) exp (−7993/T) |
TPR2 + 2-CP → IM29 via TS57 | k(T) = (4.85 × 10−14) exp (−3879/T) |
TPR2 + 2-CP → IM26 + Cl via TS58 | k(T) = (9.06 × 10−15) exp (−6757/T) |
Reactions Arrhenius Formulas | Arrhenius Formulas |
---|---|
CPDR + 2-CTP → IM30 via TS59 | k(T) = (3.33 × 10−14) exp (−2430/T) |
CPDR + 2-CTP → IM31 + Cl via TS60 | k(T) = (8.91 × 10−15) exp (−5222/T) |
CPDR + 2-CTP → IM32 via TS61 | k(T) = (2.36 × 10−15) exp (−11424/T) |
CPDR + 2-CTP → IM33 + Cl via TS62 | k(T) = (5.26 × 10−15) exp (−12811/T) |
CTPDR + 2-CTP → IM34 via TS63 | k(T) = (1.05 × 10−14) exp (−3225/T) |
CTPDR + 2-CTP → IM35 + Cl via TS64 | k(T) = (2.45 × 10−15) exp (−7902/T) |
CTPDR + 2-CTP → IM36 via TS65 | k(T) = (5.65 × 10−15) exp (−5904/T) |
CTPDR + 2-CTP → IM37 + Cl via TS66 | k(T) = (2.03 × 10−15) exp (−8446/T) |
CTPDR + 2-CP → IM38 via TS67 | k(T) = (1.43 × 10−13) exp (−3672/T) |
CTPDR + 2-CP → IM39 + Cl via TS68 | k(T) = (1.72 × 10−14) exp (−6042/T) |
CTPDR + 2-CP → IM40 via TS69 | k(T) = (1.31 × 10−14) exp (−6256/T) |
CTPDR + 2-CP → IM41 + Cl TS70 | k(T) = (1.04 × 10−14) exp (−8632/T) |
PDR + 2-CTP → IM42 via TS71 | k(T) = (3.51 × 10−14) exp (−2775/T) |
PDR + 2-CTP → IM43 + Cl via TS72 | k(T) = (4.24 × 10−15) exp (−5424/T) |
PDR + 2-CTP → IM44 via TS73 | k(T) = (6.46 × 10−15) exp (−11909/T) |
PDR + 2-CTP → IM45 + Cl TS74 | k(T) = (2.54 × 10−14) exp (−13132/T) |
TPDR + 2-CTP → IM46 via TS75 | k(T) = (1.37 × 10−14) exp (−3265/T) |
TPDR + 2-CTP → IM47 + Cl via TS76 | k(T) = (1.88 × 10−15) exp (−7484/T) |
TPDR + 2-CTP → IM48 via TS77 | k(T) = (4.21 × 10−14) exp (−6501/T) |
TPDR + 2-CTP → IM49 + Cl TS78 | k(T) = (7.95 × 10−15) exp (−8890/T) |
TPDR + 2-CP → IM50 via TS79 | k(T) = (8.93 × 10−14) exp (−3646/T) |
TPDR + 2-CP → IM51 + Cl via TS80 | k(T) = (9.45 × 10−15) exp (−5768/T) |
TPDR + 2-CP → IM52 via TS81 | k(T) = (2.02 × 10−14) exp (−6885/T) |
TPDR + 2-CP → IM53 + Cl TS82 | k(T) = (3.08 × 10−14) exp (−9091/T) |
C(T)PR1 with 2-C(T)P | C(T)PR2 and (T)PR2 with 2-C(T)P | C(T)PDR and (T)PDR with 2-C(T)P | ||||
---|---|---|---|---|---|---|
C/C type | O/C type | S/C type | C/C type | C/C type | O/C type | S/C type |
7.28 × 10−23 | 1.75 × 10−20 | 2.60 × 10−16 | 2.34 × 10−16 | 9.82 × 10−16 | 3.24 × 10−20 | 1.59 × 10−17 |
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Zuo, C.; Wang, H.; Pan, W.; Zheng, S.; Xu, F.; Zhang, Q. Quantum Chemical and Kinetic Study on Radical/Molecule Formation Mechanism of Pre-Intermediates for PCTA/PT/DT/DFs from 2-Chlorothiophenol and 2-Chlorophenol Precursors. Int. J. Mol. Sci. 2019, 20, 1542. https://doi.org/10.3390/ijms20071542
Zuo C, Wang H, Pan W, Zheng S, Xu F, Zhang Q. Quantum Chemical and Kinetic Study on Radical/Molecule Formation Mechanism of Pre-Intermediates for PCTA/PT/DT/DFs from 2-Chlorothiophenol and 2-Chlorophenol Precursors. International Journal of Molecular Sciences. 2019; 20(7):1542. https://doi.org/10.3390/ijms20071542
Chicago/Turabian StyleZuo, Chenpeng, Hetong Wang, Wenxiao Pan, Siyuan Zheng, Fei Xu, and Qingzhu Zhang. 2019. "Quantum Chemical and Kinetic Study on Radical/Molecule Formation Mechanism of Pre-Intermediates for PCTA/PT/DT/DFs from 2-Chlorothiophenol and 2-Chlorophenol Precursors" International Journal of Molecular Sciences 20, no. 7: 1542. https://doi.org/10.3390/ijms20071542