Computational Studies of Coinage Metal Anion M− + CH3X (X = F, Cl, Br, I) Reactions in Gas Phase
Abstract
:1. Introduction
2. Computational Methods
3. Results and Discussion
3.1. Reaction Enthalpies
3.2. Potential Energy Profiles
3.2.1. The Back-Side Attack Pathway
3.2.2. The Front-Side Attack at C Atom Pathway
3.2.3. The Halogen-Bonded Complex Pathway
3.2.4. Comparison between Metallic Nucleophiles M− and Main Group Nucleophiles F−
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Conflicts of Interest
References
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Products | X | F | Cl | Br | I |
---|---|---|---|---|---|
M = Cu | |||||
OI | [CH3–Cu–X]− | −64.3 | −79.8 | −81.2 | −82.1 |
SN2 | CuCH3 + X− | 4.2 | −27.1 | −31.9 | −37.6 |
XA | CuX− + CH3 | 12.3 | −5.1 | −7.2 | −9.1 |
PT | HCu + CH2X− | 62.5 | 49.8 | 46.3 | 41.4 |
M = Ag | |||||
OI | [CH3–Ag–X]− | −37.5 | −57.8 | −61.0 | −63.9 |
SN2 | AgCH3 + X− | 18.1 | −13.1 | −18.0 | −23.6 |
XA | AgX− + CH3 | 26.4 | 4.3 | 0.6 | −3.0 |
PT | HAg + CH2X− | 73.1 | 60.4 | 56.8 | 52.0 |
M = Au | |||||
OI | [CH3−Au−X]− | −38.0 | −57.3 | −60.4 | −63.6 |
SN2 | AuCH3 + X− | 21.8 | −9.5 | −14.3 | −20.0 |
XA | AuX− + CH3 | 43.7 | 20.7 | 15.9 | 10.5 |
PT | HAu + CH2X− | 77.8 | 65.1 | 61.5 | 56.6 |
X | F | Cl | Br | I | ||||
---|---|---|---|---|---|---|---|---|
E | H | E | H | E | H | E | H | |
M = Cu | ||||||||
Cu− + CH3X | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 |
RC | −6.6 | −5.0 | −8.0 | −6.5 | −8.7 | −7.2 | −9.8 | −8.7 |
invTS | 13.4 | 12.1 | −2.9 | −3.1 | −6.9 | −6.8 | −9.8 | −9.3 |
PC | 4.7 | 3.4 | −25.6 | −25.9 | −31.1 | −31.0 | −36.4 | −35.9 |
XC | - | - | - | - | −1.8 | −0.5 | −11.8 | −11.3 |
XTS | - | - | - | - | 1.3 | 2.1 | 0.4 | 1.5 |
OxTS | 33.3 | 31.7 | 24.3 | 23.5 | 19.3 | 18.8 | 14.3 | 14.1 |
MTS | 4.6 | 2.7 | −25.7 | −26.5 | - | - | - | - |
HPC | −0.7 | −2.5 | - | - | - | - | - | - |
HPTS | 0.0 | −2.1 | - | - | −32.6 | −33.0 | −38.2 | −38.3 |
M = Ag | ||||||||
Ag− + CH3X | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 |
RC | −6.4 | −4.8 | −7.7 | −6.1 | −8.3 | −6.8 | −9.3 | −7.8 |
invTS | 19.6 | 18.2 | −0.1 | −0.4 | −4.6 | −4.6 | −8.5 | −8.3 |
PC | 17.9 | 16.8 | −11.5 | −11.6 | −17.0 | −16.7 | −22.9 | −22.4 |
XC | - | - | - | - | -1.4 | 0.0 | −7.9 | −6.9 |
XTS | - | - | - | - | 1.1 | 2.4 | 0.3 | 1.5 |
OxTS | 42.0 | 40.4 | 23.7 | 22.8 | 18.2 | 17.7 | 13.6 | 13.3 |
MTS | 17.9 | 16.3 | - | - | - | - | - | - |
HPC | 13.3 | 13.2 | - | - | - | - | - | - |
HPTS | 16.1 | 14.1 | −13.8 | −14.5 | −17.7 | −18.1 | −24.6 | −24.6 |
M = Au | ||||||||
Au− + CH3X | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 |
RC | −8.6 | −7.0 | −10.0 | −8.4 | −10.6 | −9.0 | −11.1 | −9.6 |
invTS | 14.2 | 13.6 | −2.7 | −2.5 | −6.7 | −6.3 | −9.6 | −9.1 |
PC | 12.5 | 12.0 | −15.1 | −14.5 | −20.2 | −19.3 | −25.6 | −24.5 |
XC | - | - | - | - | −3.3 | −1.8 | −11.0 | −10.0 |
XTS | - | - | - | - | 0.7 | 1.9 | −0.3 | 0.8 |
OxTS | 48.2 | 47.2 | 36.2 | 35.8 | 31.1 | 31.0 | 27.2 | 27.1 |
MTS | 12.9 | 11.7 | −14.7 | −14.8 | - | - | - | - |
HPC | 10.3 | 9.0 | −14.7 | −14.2 | - | - | - | - |
HPTS | 13.1 | 11.7 | −14.0 | −14.1 | −19.2 | −18.9 | −24.4 | −23.8 |
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Wang, F.; Ji, X.; Ying, F.; Zhang, J.; Zhao, C.; Xie, J. Computational Studies of Coinage Metal Anion M− + CH3X (X = F, Cl, Br, I) Reactions in Gas Phase. Molecules 2022, 27, 307. https://doi.org/10.3390/molecules27010307
Wang F, Ji X, Ying F, Zhang J, Zhao C, Xie J. Computational Studies of Coinage Metal Anion M− + CH3X (X = F, Cl, Br, I) Reactions in Gas Phase. Molecules. 2022; 27(1):307. https://doi.org/10.3390/molecules27010307
Chicago/Turabian StyleWang, Fan, Xiaoyan Ji, Fei Ying, Jiatao Zhang, Chongyang Zhao, and Jing Xie. 2022. "Computational Studies of Coinage Metal Anion M− + CH3X (X = F, Cl, Br, I) Reactions in Gas Phase" Molecules 27, no. 1: 307. https://doi.org/10.3390/molecules27010307