Theoretical Description of R–X⋯NH3 Halogen Bond Complexes: Effect of the R Group on the Complex Stability and Sigma-Hole Electron Depletion
Abstract
:1. Introduction
2. Results and Discussion
2.1. Relative Stability of the R–X⋯NH3 Systems
2.2. KLD Analysis of R-Br⋯NH3 Systems
2.3. KLD Analysis of [BrCN]n Chains
3. Models and Methods
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Conflicts of Interest
References
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Halogen Bond Donor | R Substituent | DX⋯N | ΔqN | ΔqX | ΔqxN | BEDFT | BEMP2 | BECCSD(T) |
---|---|---|---|---|---|---|---|---|
Cl | Cl | 2.52 (2.58) | 0.04 (0.00) | 0.00 (0.05) | −0.10 (−0.10) | 7.0 (7.9) | 4.4 (6.0) | 3.8 |
CF3 | 2.97 (3.01) | −0.01 (−0.01) | 0.03 (0.04) | −0.02 (−0.02) | 2.8 (3.2) | 2.5 (3.3) | 2.5 | |
CHF2 | 3.05 (3.10) | −0.01 (−0.01) | 0.03 (0.04) | −0.02 (−0.02) | 1.7 (2.0) | 1.5 (2.1) | 1.5 | |
CH2F | 3.24 (3.28) | 0.00 (0.00) | 0.01 (0.01) | −0.01 (−0.01) | 1.0 (1.2) | 0.7 1.3) | 0.7 | |
CH3 | 3.27 (3.37) | 0.00 (0.00) | 0.02 (0.03) | −0.01 (−0.01) | −0.1 (0.0) | −0.4 (−0.1) | −0.3 | |
Br | Br | 2.55 (2.50) | 0.04 (0.01) | 0.02 (0.08) | −0.14 (−0.17) | 8.7 (12.4) | 7.0 (11.5) | 5.0 |
CF3 | 2.88 (2.91) | −0.01 (−0.02) | 0.03 (0.05) | −0.03 (−0.03) | 4.9 (7.1) | 3.9 (6.5) | 3.9 | |
CHF2 | 2.99 (3.03) | −0.01 (−0.01) | 0.04 (0.05) | −0.03 (−0.03) | 3.5 (5.2) | 2.6 (4.7) | 2.6 | |
CH2F | 3.05 (3.11) | 0.00 (−0.01) | 0.03 (0.04) | −0.02 (−0.03) | 2.4 (4.0) | 1.6 (3.4) | 1.6 | |
CH3 | 3.08 (3.17) | 0.00 (0.00) | 0.03 (0.04) | −0.02 (−0.03) | 1.5 (3.0) | 0.6 (2.2) | 0.6 | |
I | I | 2.58 (2.62) | 0.08 (0.02) | 0.06(0.13) | −0.23 (−0.25) | 16.4 (17.2) | 10.6 (12.7) | 8.7 |
CF3 | 2.80 (2.84) | 0.03 (−0.01) | 0.01 (0.05) | −0.04 (−0.04) | 11.8 (12.3) | 9.5 (10.7) | 8.9 | |
CHF2 | 2.94 (3.01) | 0.03 (0.00) | 0.03 (0.06) | −0.04 (−0.04) | 7.7 (8.1) | 5.7 (6.7) | 5.4 | |
CH2F | 3.07 (3.15) | 0.02 (0.00) | 0.03 (0.06) | −0.04 (−0.04) | 5.1 (5.5) | 3.4 (4.2) | 3.2 | |
CH3 | 3.14 (3.26) | 0.02 (0.00) | 0.03 (0.05) | −0.04 (−0.04) | 3.5 (3.9) | 1.8 (2.5) | 1.6 |
Halogen Bond Donor | R Substituent | BEMP2 | Pop (Br) | |
---|---|---|---|---|
Br | Br | 7.0 | 0.194 | 5.56 |
CF3 | 3.9 | 0.259 | 5.64 | |
CHF2 | 2.6 | 0.269 | 5.69 | |
CH2F | 1.6 | 0.275 | 5.73 | |
CH3 | 0.6 | 0.271 | 5.75 | |
CH3CH2 | 0.3 | 0.278 | 5.78 | |
CH2CH | 1.2 | 0.270 | 5.77 | |
CHC | 3.6 | 0.249 | 5.59 |
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Zurita, J.; Rodriguez, V.; Zambrano, C.; Mora, J.R.; Rincón, L.; Torres, F.J. Theoretical Description of R–X⋯NH3 Halogen Bond Complexes: Effect of the R Group on the Complex Stability and Sigma-Hole Electron Depletion. Molecules 2020, 25, 530. https://doi.org/10.3390/molecules25030530
Zurita J, Rodriguez V, Zambrano C, Mora JR, Rincón L, Torres FJ. Theoretical Description of R–X⋯NH3 Halogen Bond Complexes: Effect of the R Group on the Complex Stability and Sigma-Hole Electron Depletion. Molecules. 2020; 25(3):530. https://doi.org/10.3390/molecules25030530
Chicago/Turabian StyleZurita, Juan, Vladimir Rodriguez, Cesar Zambrano, Jose Ramón Mora, Luis Rincón, and F. Javier Torres. 2020. "Theoretical Description of R–X⋯NH3 Halogen Bond Complexes: Effect of the R Group on the Complex Stability and Sigma-Hole Electron Depletion" Molecules 25, no. 3: 530. https://doi.org/10.3390/molecules25030530