Effects of Methyl Substitution and Leaving Group on E2/SN2 Competition for Reactions of F− with RY (R = CH3, C2H5, iC3H7, tC4H9; Y = Cl, I)
Abstract
:1. Introduction
2. Results and Discussion
2.1. Potential Energy Surfaces of F− + RY Reactions
2.2. Effects of α-Methyl Substitution
2.3. Effects of Leaving Group
3. Computational Methods
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
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Cl | I | ||||||
---|---|---|---|---|---|---|---|
R | Species | MP2 | CCSD(T) a | Exptl c | MP2 | CCSD(T) b | Exptl c |
CH3 | 1dRCH | 16.9 | 17.6 | −18.9 | −20.3 | ||
1TSRC | −15.1 | −15.8 | −15.8 | −17.6 | |||
1bRC | −15.6 | −16.1 | −16.2 | −18.3 | |||
1bTS | −12.3 | −12.8 | −15.6 | −18.1 | |||
1dTS | 32.1 | 30.7 | 22.8 | 18.3 | |||
1dPC | −40.7 | −41.6 | −49.6 | −55.3 | |||
1bPC | −40.7 | −41.6 | −49.6 | −55.3 | |||
1P2 | −30.6 | −31.8 | −31.1 | −40.9 | −48.0 | −42.3 | |
C2H5 | 2c/2dRCH | −17.8 | −18.0 | −18.7 | −19.6 | ||
2a/2bRC | −17.5 | −17.7 | −19.4 | −20.1 | |||
2aTS | −11.2 | −11.1 | −15.8 | −16.0 | |||
2bTS | −11 | −11.3 | −15.4 | −16.9 | |||
2cTS | −0.1 | −6.8 | −4.2 | −4.9 | |||
2dTS | 31.1 | 30.0 | 21.5 | 19.2 | |||
2aPC | −31.9 | −33.6 | −41.5 | −42.7 | |||
2bPC | −42.4 | −44.6 | −51.8 | −50.9 | |||
2cPC | −44.2 | −41.6 | −49.0 | −54.0 | |||
2dPC | −42.4 | −44.6 | −51.8 | −54.0 | |||
2P1 | −15.5 | −18.1 | −22.5 | −26.3 | −26.2 | −37.8 | |
2P2 | −31.3 | −34.0 | −32.0 | −42.1 | −44.0 | −48.7 | |
iC3H7 | 3a/3bRC | −20.7 | −21.4 | −21.9 | −22.8 | ||
3c/3dRC | −15.5 | −16.3 | −16.9 | −17.9 | |||
3aTS | −11.6 | −12.4 | −16.9 | −17.5 | |||
3bTS | −9.1 | −11.0 | −14.1 | −16.3 | |||
3cTS | 0.3 | −1.0 | −4.3 | −5.4 | |||
3dTS | 31.5 | 28.8 | 21.4 | - | |||
3aPC | −31.8 | −33.8 | −41.8 | −44.4 | |||
3bPC | −43.9 | −46.9 | −54.0 | −57.9 | |||
3cPC | −44.4 | −47.3 | −48.8 | −52.8 | |||
3dPC | −44.4 | −47.3 | −54.0 | - | |||
3P1 | −13.9 | −16.5 | −22.1 | −24.8 | −28.4 | −37.7 | |
3P2 | −31.8 | −34.9 | −30.3 | −42.8 | −46.8 | −45.9 | |
tC4H9 | 4a/4bRC | −23.1 | −23.3 | −24.4 | −25.6 | ||
4c/4dRC | −15.6 | −16.1 | −17.2 | −17.8 | |||
4aTS | −11.9 | −17.6 | −17.7 | −24.4 | |||
4bTS | −2.3 | - | −7.5 | - | |||
4cTS | 0.8 | −4.6 | −3.9 | −10.8 | |||
4dTS | 39.9 | - | 28.8 | - | |||
4aPC | −33.4 | −37.8 | −43.4 | −51.2 | |||
4bPC | −46.2 | - | −56.1 | - | |||
4cPC | −44.0 | −49.1 | −49.1 | −57.4 | |||
4dPC | −46.2 | - | −56.1 | - | |||
4P1 | −12.6 | −18.2 | −22.1 | −23.9 | −37.6 | −37.6 | |
4P2 | −31.9 | - | −29.5 | −43.3 | - | −37.8 |
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Zhen, W.; Zhao, S.; Fu, G.; Wang, H.; Sun, J.; Yang, L.; Zhang, J. Effects of Methyl Substitution and Leaving Group on E2/SN2 Competition for Reactions of F− with RY (R = CH3, C2H5, iC3H7, tC4H9; Y = Cl, I). Molecules 2023, 28, 6269. https://doi.org/10.3390/molecules28176269
Zhen W, Zhao S, Fu G, Wang H, Sun J, Yang L, Zhang J. Effects of Methyl Substitution and Leaving Group on E2/SN2 Competition for Reactions of F− with RY (R = CH3, C2H5, iC3H7, tC4H9; Y = Cl, I). Molecules. 2023; 28(17):6269. https://doi.org/10.3390/molecules28176269
Chicago/Turabian StyleZhen, Wenqing, Siwei Zhao, Gang Fu, Hongyi Wang, Jianmin Sun, Li Yang, and Jiaxu Zhang. 2023. "Effects of Methyl Substitution and Leaving Group on E2/SN2 Competition for Reactions of F− with RY (R = CH3, C2H5, iC3H7, tC4H9; Y = Cl, I)" Molecules 28, no. 17: 6269. https://doi.org/10.3390/molecules28176269