Participation of Phosphorylated Analogues of Nitroethene in Diels–Alder Reactions with Anthracene: A Molecular Electron Density Theory Study and Mechanistic Aspect
Abstract
:1. Introduction
2. Computational Details
3. Results and Discussion
3.1. Analysis of the CDFT Reactivity Indices and ELF Characterization of the Reactants
3.2. DA Reaction Profiles of the bis(2-chloroethyl) 2-nitro- 1a and bis(2-chloroethyl) 2-bromo-2-Nitroethenylphosphonates 1b with Anthracene 2
3.3. BET Study of the DA Reaction between bis(2-chloroethyl) 2-nitro-ethenylphosphonate 1a and Anthracene 2
4. Conclusions
Supplementary Materials
Funding
Acknowledgments
Conflicts of Interest
References
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µ | η | ω | N | |
---|---|---|---|---|
1a | −5.59 | 5.19 | 3.01 | 0.94 |
1b | −5.62 | 4.74 | 3.33 | 1.13 |
2 | −3.43 | 3.59 | 1.64 | 3.89 |
Transition | ΔH353 | ΔG353 | ΔS353 |
---|---|---|---|
1+2→MC1 | −2.1 | 7.9 | −33.7 |
1+2→TS1 | 21.8 | 36.8 | −50.4 |
1+2→3a | −13.6 | 1.5 | −50.7 |
1+2→MC2 | −3.6 | 4.8 | −28.0 |
1+2→TS2 | 18.7 | 35.2 | −55.3 |
1+2→3b | −15.0 | 3.8 | −63.0 |
Structure | C2-C3 | C1-C6 | Δl | GEDT [e] | Imaginary Frequency [cm−1] | ||
---|---|---|---|---|---|---|---|
r [Å] | l | r [Å] | l | ||||
MC1 | 6.816 | 3.925 | |||||
TS1 | 2.106 | 0.664 | 2.430 | 0.448 | 0.22 | 0.30 | −399.48 |
3a | 1.576 | 1.566 | |||||
MC2 | 7.256 | 5.187 | |||||
TS2 | 1.958 | 0.762 | 2.805 | 0.203 | 0.56 | 0.36 | −332.75 |
3b | 1.581 | 1.561 |
Points | 1a | 2 | MC1 | P1 | P2 | P3 | P4 | P5 | P6 | P7 | 3a | TS1 |
---|---|---|---|---|---|---|---|---|---|---|---|---|
Phases | I | II | III | IV | V | VI | VII | VIII | ||||
d(C2-C3) | 3.489 | 2.659 | 2.502 | 2.449 | 2.412 | 2.356 | 2.316 | 2.184 | 1.566 | 2.430 | ||
d(C1-C6) | 3.643 | 2.429 | 2.208 | 2.132 | 2.081 | 2.005 | 1.956 | 1.821 | 1.576 | 2.106 | ||
ΔE | 0.0 | 8.5 | 17.1 | 22.0 | 21.8 | 15.8 | 5.5 | −2.7 | −11.5 | 24.0 | ||
V(C1,C2) | 1.74 | 1.75 | 3.32 | 3.19 | 2.95 | 2.69 | 2.55 | 2.45 | 2.22 | 1.99 | 2.87 | |
V’(C1,C2) | 1.74 | 1.69 | ||||||||||
V(C3,C4) | 2.71 | 2.81 | 2.65 | 2.58 | 2.55 | 2.53 | 2.49 | 2.45 | 2.33 | 2.05 | 2.54 | |
V(C4,C5) | 2.47 | 2.45 | 2.59 | 2.60 | 2.61 | 2.62 | 2.65 | 2.66 | 2.70 | 2.75 | 2.61 | |
V(C5,C6) | 2.71 | 2.79 | 2.65 | 2.50 | 2.40 | 2.35 | 2.29 | 2.23 | 2.16 | 2.05 | 2.37 | |
V(C6,C7) | 2.93 | 2.83 | 2.69 | 2.53 | 2.46 | 2.41 | 2.34 | 2.31 | 2.22 | 2.07 | 2.44 | |
V(C7,C8) | 2.47 | 2.48 | 2.54 | 2.60 | 2.61 | 2.62 | 2.64 | 2.65 | 2.69 | 2.77 | 2.61 | |
V(C8,C3) | 2.93 | 2.81 | 2.76 | 2.69 | 2.64 | 2.61 | 2.61 | 2.47 | 2.33 | 2.06 | 2.61 | |
V(C3) | 0.13 | 0.23 | 0.32 | 0.28 | ||||||||
V(C2) | 0.34 | 0.45 | 0.40 | |||||||||
V(C1) | 0.38 | 0.50 | 0.57 | |||||||||
V(C2,C3) | 0.96 | 1.07 | 1.38 | 1.76 | ||||||||
V(C6) | 0.15 | |||||||||||
V(C1,C6) | 1.02 | 1.79 |
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Kącka-Zych, A. Participation of Phosphorylated Analogues of Nitroethene in Diels–Alder Reactions with Anthracene: A Molecular Electron Density Theory Study and Mechanistic Aspect. Organics 2020, 1, 36-48. https://0-doi-org.brum.beds.ac.uk/10.3390/org1010004
Kącka-Zych A. Participation of Phosphorylated Analogues of Nitroethene in Diels–Alder Reactions with Anthracene: A Molecular Electron Density Theory Study and Mechanistic Aspect. Organics. 2020; 1(1):36-48. https://0-doi-org.brum.beds.ac.uk/10.3390/org1010004
Chicago/Turabian StyleKącka-Zych, Agnieszka. 2020. "Participation of Phosphorylated Analogues of Nitroethene in Diels–Alder Reactions with Anthracene: A Molecular Electron Density Theory Study and Mechanistic Aspect" Organics 1, no. 1: 36-48. https://0-doi-org.brum.beds.ac.uk/10.3390/org1010004