Understanding the Reactivity of Trimethylsilyldiazoalkanes Participating in [3+2] Cycloaddition Reactions towards Diethylfumarate with a Molecular Electron Density Theory Perspective
Abstract
:1. Introduction
2. Computational Methods
3. Results and Discussion
3.1. ELF Topological Analysis of Trimethylsilyldiazoalkanes TSDE 1, TSDP 2, and TSDA 3, and Diethyl Fumarate DFM 4
3.2. Analysis of the CDFT Indices of the Reactants
3.3. Analysis of the Energy Profile of the Stationary Points along the Feasible Reaction Paths for 32CA Reactions of TSDE 1, TSDP 2, and TSDA 3, with DFM 4
3.4. BET Study of the 32CA Reaction of TSDE 1 and TSDA 3 with DFM 4
3.5. ELF Topological Analysis at the TSs
3.6. QTAIM and IGM Topological Analysis at TSs
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Conflicts of Interest
References
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1 | 2 | 3 | 4 | |
---|---|---|---|---|
V(N1) | 3.82 | 3.74 | 3.63 | |
V(N1,N2) | 1.79 | 1.81 | 1.89 | |
V’(N1,N2) | 1.90 | 1.91 | 1.97 | |
V(C3,N2) | 3.07 | 3.06 | 2.93 | |
V(C3,C6) | 1.87 | 2.17 | 2.36 | |
V(C3,Si) | 3.19 | 3.07 | 3.11 | |
V(C4,C5) | 1.67 | |||
V’(C4,C5) | 1.65 |
μ | η | ω | N | |
---|---|---|---|---|
1 | −3.12 | 4.60 | 1.06 | 3.70 |
2 | −3.22 | 4.11 | 1.27 | 3.84 |
3 | −3.89 | 4.84 | 1.56 | 2.80 |
4 | −4.84 | 5.39 | 2.18 | 1.58 |
Gas Phase | CCl4 | |||||||||
---|---|---|---|---|---|---|---|---|---|---|
∆E | ∆H | ∆S | ∆G | GEDT | ∆E | ∆H | ∆S | ∆G | GEDT | |
TS1 | 9.4 | 10.4 | −58.6 | 27.9 | 0.27 | 9.7 | 10.3 | −55.5 | 26.8 | 0.28 |
5 | −32.4 | −29.4 | −61.3 | −11.2 | −32.5 | −29.4 | −61.8 | −11.0 | ||
TS2 | 7.6 | 8.1 | −56.1 | 24.9 | 0.26 | 7.6 | 8.0 | −55.7 | 24.6 | 0.27 |
6 | −32.3 | −29.5 | −54.7 | −13.3 | −32.4 | −29.7 | −55.1 | −13.2 | ||
TS3 | 14.0 | 14.4 | −52.1 | 29.9 | 0.23 | 14.5 | 14.7 | −52.5 | 30.4 | 0.24 |
7 | −28.0 | −25.9 | −59.2 | −8.2 | −27.4 | −25.4 | −58.6 | −8.0 | ||
TS4 | 11.3 | 10.8 | −53.4 | 26.7 | 0.21 | 11.6 | 11.8 | −53.6 | 27.8 | 0.22 |
8 | −25.8 | −24.6 | −62.8 | −5.9 | −25.7 | −24.5 | −63.1 | −5.7 | ||
TS5 | 18.6 | 19.0 | −51.8 | 34.4 | 0.19 | 19.3 | 19.7 | −50.8 | 34.9 | 0.20 |
9 | −20.3 | −17.7 | −49.6 | −2.9 | −20.5 | −17.9 | −49.9 | −3.1 | ||
TS6 | 15.6 | 15.2 | −54.5 | 31.4 | 0.19 | 16.4 | 16.5 | −51.0 | 31.7 | 0.20 |
10 | −21.4 | −19.6 | −54.0 | −3.5 | −21.6 | −19.8 | −55.1 | −3.3 |
TS1 | TS2 | TS3 | TS4 | TS5 | TS6 | |
---|---|---|---|---|---|---|
V(N1) | 3.57 | 3.60 | 3.57 | 3.59 | 3.52 | 3.52 |
V(N1,N2) | 1.53 | 1.44 | 1.44 | 1.31 | 1.55 | 1.55 |
V’(N1,N2) | 1.63 | 1.67 | 1.69 | 1.72 | 1.56 | 1.55 |
V(N2) | 1.76 | 1.82 | 1.82 | 1.94 | 1.85 | 1.88 |
V(C3,N2) | 2.07 | 2.07 | 2.05 | 2.05 | 2.05 | 2.03 |
V(C3,C6) | 1.91 | 1.92 | 2.13 | 2.19 | 2.41 | 2.30 |
V(C3,Si) | 2.27 | 2.28 | 2.25 | 2.28 | 2.31 | 2.29 |
V(C4,C5) | 2.94 | 2.96 | 2.95 | 2.93 | 2.91 | 2.91 |
V(C3) | 0.67 | 0.63 | 0.62 | 0.55 | 0.62 | 0.62 |
V(C4) | 0.23 | 0.18 | 0.19 | 0.20 | 0.23 | 0.20 |
CP1 (C3-C4) | CP2 (N1-C5) | |||||
---|---|---|---|---|---|---|
ρ | ρ | |||||
TS1 | 0.072 | 0.031 | −0.020 | 0.051 | 0.091 | −0.005 |
TS2 | 0.066 | 0.036 | −0.017 | 0.058 | 0.091 | −0.008 |
TS3 | 0.069 | 0.036 | −0.018 | 0.056 | 0.092 | −0.007 |
TS4 | 0.063 | 0.037 | −0.016 | 0.070 | 0.091 | −0.014 |
TS5 | 0.073 | 0.030 | −0.021 | 0.062 | 0.092 | −0.010 |
TS6 | 0.073 | 0.031 | −0.020 | 0.064 | 0.091 | −0.011 |
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Domingo, L.R.; Acharjee, N.; Mohammad-Salim, H.A. Understanding the Reactivity of Trimethylsilyldiazoalkanes Participating in [3+2] Cycloaddition Reactions towards Diethylfumarate with a Molecular Electron Density Theory Perspective. Organics 2020, 1, 3-18. https://0-doi-org.brum.beds.ac.uk/10.3390/org1010002
Domingo LR, Acharjee N, Mohammad-Salim HA. Understanding the Reactivity of Trimethylsilyldiazoalkanes Participating in [3+2] Cycloaddition Reactions towards Diethylfumarate with a Molecular Electron Density Theory Perspective. Organics. 2020; 1(1):3-18. https://0-doi-org.brum.beds.ac.uk/10.3390/org1010002
Chicago/Turabian StyleDomingo, Luis R., Nivedita Acharjee, and Haydar A. Mohammad-Salim. 2020. "Understanding the Reactivity of Trimethylsilyldiazoalkanes Participating in [3+2] Cycloaddition Reactions towards Diethylfumarate with a Molecular Electron Density Theory Perspective" Organics 1, no. 1: 3-18. https://0-doi-org.brum.beds.ac.uk/10.3390/org1010002