Electronic structure theory study of the reactivity and structural molecular properties of halo-substituted (F, Cl, Br) and heteroatom (N, O, S) doped cyclobutane
-
Moses M. Edim
,
Emmanuel A. Bisong
Abstract
Cyclobutane and its halo-substituted derivatives and its heteroatom doped derivatives have been extensively investigated in this study because of the vast applications and interesting chemistry associated with them, the vibrational assignments, Natural Bond Orbital (NBO) analysis, Conceptual Density Functional Theory, Quantum Mechanical Descriptors and Molecular Electrostatic Potential (MEP) analysis have been explored in this study. The corresponding wavenumbers of the studied compounds have as well been assigned by Potential Energy Distribution analysis. Several inter and intramolecular hyperconjugative interactions within the studied compounds have been revealed by the NBO analysis with a confirmation of geometric hybridization and electronic occupancy. The compounds reactivity was observed to decrease down the halo group in manners such as the stability, both were observed to decrease from azetidine to thietane. The distribution of charge was observed to be affected by the ring substituent as observed from the charge population analysis; in addition, adjacent atoms are very much affected by the inherent properties of the substituted atoms. The NBO result suggests that the molecules are stabilized by lone pair delocalization of electrons from the substituted atoms and molecular electrostatic potential (MEP) studies revealed that substituted halogens and doped heteroatoms are important and most probable sites of electrostatic interactions.
Acknowledgment
This research was not funded. Our sincere appreciation goes to Emmanuel A. Bisong for the information about the conference proceedings.
-
Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
-
Research funding: None declared.
-
Conflict of interest statement: All authors unanimously declare zero conflict of interest.
References
1. Sakhaee, N, Sakhaee, S. Pseudorotation in cyclooctane, using spherical conformational landscape model. Comput Theor Chem 2020;1184:112845. https://doi.org/10.1016/j.comptc.2020.112845.Search in Google Scholar
2. Hu, YJ, Li, LX, Han, JC, Min, L, Li, CC. Recent advances in the total synthesis of natural products containing eight-membered carbocycles (2009–2019). Chem Rev 2020;120:5910–53. https://doi.org/10.1021/acs.chemrev.0c00045.Search in Google Scholar PubMed
3. Martins, SO, Edna MaO, AR, Joseph, P, Jorge, C, lyndon, A, Cornelius, M, et al.. Synthesis of cyclobutane-fused tetracycic scaffolds via visible-light photocatalysis for building molecular complexity. J Am Chem Soc 2020;142:3094–103.10.1021/jacs.9b12129Search in Google Scholar
4. Willstätter, R, Bruce, J. “Zur Kenntnis der Cyclobutanreihe” [On our knowledge of the cyclobutane series]. Ber Dtsch Chem Ges 1907;40:3979–99. https://doi.org/10.1002/cber.19070400407.Search in Google Scholar
5. de Meijere, A, editor. Carbocyclic four-membered ring compounds. In: Houben–Weyl methods of organic chemistry, vol 17e/r. Stuttgart: Thieme; 1997.10.1055/b-0035-112718Search in Google Scholar
6. Zhang, X, Nie, Y, Yuan, Y, Lu, F, Geng, Z. Density functional theory investigation on the mechanism of dehydrogenation of cyclohexane catalyzed by heteronuclear NiTi. J Comput Theor Chem 2020;1184:112820. https://doi.org/10.1021/acs.chemrev.0c00045.Search in Google Scholar
7. Pande, JV, Bindwal, AB, Pakande, YB, Biniwale, RB. Application of microwave synthesized Ag–Rh nanoparticles in cyclohexane dehydrogenation for enhanced H2 delivery. Int J Hydrogenation Energy 2018;43:7411–23. https://doi.org/10.1016/j.ijhydene.2018.02.105.Search in Google Scholar
8. Frisch, MJ, Trucks, GW, Schlegel, HB, Scuseria, GE, Robb, MA, Cheeseman, JR, et al.. Gaussian 09, Revision C. 02. Wallingford CT: Gaussian, Inc.; 2009.Search in Google Scholar
9. Dennington, RD, Keith, TA, Millam, JM. GaussView 6.0. 16, Semichem. Inc., Shawnee Mission KS; 2016.Search in Google Scholar
10. Jamroz, MH. Vibrational energy distribution analysis. Warsaw: VEDA4; 2004. p. 2004–10.Search in Google Scholar
11. Sanchez-Marquez, J, Zorrilla, D, Sanchez-Coronilla, A, Desiree, M, Navas, J, Fernandez-Lorenzo, C, et al.. Introducing “UCA FUKUI software; reactivity-index calculations”. J Mol Model 2004;20:2492.10.1007/s00894-014-2492-1Search in Google Scholar
12. Tian, L, Feiwu, CM. A multifunctional analyzer. J Comput Chem 2012;33:580–92. https://doi.org/10.1002/jcc.21992.Search in Google Scholar PubMed
13. Yu, HS, He, X, Truhlar, DG. MN15: a new local exchange-correlation functional for Kohn–Sham density functional theory with broad accuracy for atoms, molecules, and solids. J Chem Theor Comput 2016;12:1280–93. https://doi.org/10.1021/acs.jctc.5b01082.Search in Google Scholar PubMed
14. Roeges, NPG. A guide to complete interpretation of infrared spectra of organic structures. New York: Wiley; 1994.Search in Google Scholar
15. Scortt, AP, Radom, L. Harmonic vibrational frequencies: an evaluation of Hartree–Fock, Moller–Plesset, quadratic configuration interaction, density functional theory, and semiempirical scale factors. J Phys Chem 1996;100:16502–13.10.1021/jp960976rSearch in Google Scholar
16. Kesharwani, MK, Brauer, B, Martin, JML. Frequency and zero-point vibrational energy scale factors for double-hybrid density functionals (and other selected methods): can anharmonic force fields be avoided? J Phys Chem 2015;119:1701–14. https://doi.org/10.1021/jp508422u.Search in Google Scholar PubMed
17. Houriez, C, Ferre, N, Flament, JP, Masella, M, Siri, D. Electronic basis of the comparable hydrogen bond properties of small H2CO/(H2O)n and H2NO/(H2O)n systems (n = 1, 2). J Phys Chem 2007;111:11673–82. https://doi.org/10.1021/jp075136z.Search in Google Scholar PubMed
18. Bisong, EA, Louis, H, Unimuke, TO, Odey, JO, Ubana, EI, Edim, MM, et al.. Vibrational, electronic, spectroscopic properties, and NBO analysis of P-xylene, 3,6-difluoro-p-xylee, 3,5-dichloro-p-xylene and 3,6-dibromo-p-xylene: DFT study. Heliyon 2020;6:e05783. https://doi.org/10.1016/j.heliyon.2020.e05783.Search in Google Scholar PubMed PubMed Central
19. Venkatesh, G, Govidaraju, M, Kamal, C, Vennila, P, Kaya, S. Structural, electronic and optical properties of 2,5-dichloro-p-xylene: experimental and theoretical calculations using DFT method. RSC Adv 2017;7:1401. https://doi.org/10.1039/c6ra25535c.Search in Google Scholar
20. Ahmad, MS, Khalid, M, Shaheen, MA, Tahir, MN, Khan, MU, Braga, AAC, et al.. Synthesis and XRD, FT-IR vibrational, UV–vis, and nonlinear optical exploration of novel tetra substituted imidazole derivatives: a synergistic experimental–computational analysis. J Phys Chem Solid 2018;115:265–76. https://doi.org/10.1016/j.jpcs.2017.12.054.Search in Google Scholar
21. Khalid, M, Ullah, MA, Adeel, M, Khan, MU, Tahir, MN, Braga, AAC. Synthesis, crystal structure analysis, spectral IR, UV–Vis, NMR assessments, electronic and nonlinear optical properties of potent quinoline based derivatives: interplay of experimental and DFT study. J Saudi Chem Soc 2019;23:546–60. https://doi.org/10.1016/j.jscs.2018.09.006.Search in Google Scholar
22. Khan, MU, Ibrahim, M, Khalid, M, Jamil, S, Al-Saadi, AA, Janjua, MRSA. Quantum chemical designing of indolo [3, 2, 1-jk] carbazole-based dyes for highly efficient nonlinear optical properties. Chem Phys Lett 2019;719:59–66. https://doi.org/10.1016/j.cplett.2019.01.043.Search in Google Scholar
23. Shimanouchi, T. Tables of vibrational frequencies, consolidated, vol. I. National Bureau of Standards; 1972.10.6028/NBS.NSRDS.39Search in Google Scholar
24. Karnan, M, Balachandran, V, Murugan, M, Murali, MK, Nataraj, A. Vibrational (FT-IR and FT-Raman) spectra, NBO, HOMO–LUMO, Molecular electrostatic potential surface and computational analysis of 4-(trifluoromethyl) benzylbromide. Spectrochim Acta Mol Biomol Spectrosc 2013;116:84–95. https://doi.org/10.1016/j.saa.2013.06.120.Search in Google Scholar PubMed
25. Raub, S, Jansen, G. A quantitative measure of bond polarity from the electron localization function and the theory of atoms in molecules. Theor Chem Acc 2001;106:223–32. https://doi.org/10.1007/s002140100268.Search in Google Scholar
26. Allen, LC, Egolf, DA, Knight, ET, Liang, C. Bond polarity index. J Phys Chem 1990;94:5602–7. https://doi.org/10.1021/j100377a037.Search in Google Scholar
27. Klein, J, Khartabil, H, Boisson, J-C, Contreras-García, J, Piquemal, J-P, Hénon, E. New way for probing bond strength. J Phys Chem 2020;124:1850–60. https://doi.org/10.1021/acs.jpca.9b0984.Search in Google Scholar
28. Domingo, LR, Rios-Gutierrez, M, Perez, P. Applications of the conceptual density functional theory indices to organic chemistry reactivity. Molecules 2016;21:748. https://doi.org/10.3390/molecules21060748.Search in Google Scholar PubMed PubMed Central
29. Cao, J, Ren, Q, Chen, F, Lu, T. Comparative study of the methods for predicting the reactive site of nucleophilic reaction. Sci China Chem 2015;58:1845–52. https://doi.org/10.1007/s11426-015-5494-7.Search in Google Scholar
30. Morell, C, Grand, A, Toro-Labbe, A. New dual descriptor for chemical reactivity. J Phys Chem 2004;109:205–12.10.1021/jp046577aSearch in Google Scholar
31. Wang, B, Rong, C, Chattaraj, PK, Liu, S. A comparative study to predict regioselectivity, electrophilicity and nucleophilicity with Fukui function and Hirshfeld charge. Theor Chem Acc 2019;138:124. https://doi.org/10.1007/s00214-019-2515-1.Search in Google Scholar
32. Parr, RG, Yang, W. Density functional theory of atoms and molecules. New York, NY, USA: Oxford University Press; 1989.Search in Google Scholar
33. Parr, RG, Pearson, RG. Absolute hardness: companion parameter to absolute electronegativity. J Am Chem Soc 1983;105:7512–6. https://doi.org/10.1021/ja00364a005.Search in Google Scholar
34. Parr, RG, Szentpaly, LV, Liu, S. Electrophilicity index. J Am Chem Soc 1999;121:1922–4. https://doi.org/10.1021/ja983494x.Search in Google Scholar
35. Vennila, P, Govindaraju, M, Venkatesh, G, Kamal, C, Mary, SY, Panicker, CY, et al.. A complete computational and spectroscopic study of 2-bromo-1,4-dichlorobenzene-A frequently used benzene derivative. J Mol Struct 2018;1151:245–55. https://doi.org/10.1016/J.molstruc.2017.09.049.Search in Google Scholar
36. Koopmans, T. Über die Zuordnung von Wellenfunktionen und Eigenwerten zu deninzelnen Elektronen Eines Atoms. Physica 1934;1:104–13. https://doi.org/10.1016/s0031-8914(34)90011-2.Search in Google Scholar
37. Pearson, RG. Hard and soft acids and bases. J Am Chem Soc 1963;85:3533–5339. https://doi.org/10.1021/ja00905a001.Search in Google Scholar
38. Pearson, RG. Absolute electronegativity and hardness: application to inorganic chemistry. Inorg Chem 1988;27:734–40. https://doi.org/10.1021/ic00277a030.Search in Google Scholar
39. Pearson, RG. Absolute electronegativity and hardness correlated with molecular orbital theory. Proc Natl Acad Sci USA 1986;83:8440–1. https://doi.org/10.1073/pnas.83.22.8440.Search in Google Scholar PubMed PubMed Central
40. Dunnington, BD, Schmidt, JR. Generalization of natural bond orbital analysis of periodic systems: applications to solids and surfaces via plane-wave density functional theory. J Chem Theor Comput 2012;8:1902–11. https://doi.org/10.1021/ct300002t.Search in Google Scholar PubMed
41. Rubarani, PG, Sampath, KS. Natural bond orbital (NBO) population analysis of 1-azanapthalene-8-ol. ACTA Physica Polonica A 2014;125:18–22. https://doi.org/10.12693/APhysPoIA.125.18.Search in Google Scholar
42. Lu, T, Chen, F. Atomic dipole moment corrected Hirshfeld population method. J Theor Comput Chem 2012;11:163–83. https://doi.org/10.1142/s0219633612500113.Search in Google Scholar
43. Polistzer, P, Murray, JS. The fundamental nature and role of the electrostatic potential in atoms and molecules. Theor Chem Acc 2002;108:132–42.10.1007/s00214-002-0363-9Search in Google Scholar
© 2021 Walter de Gruyter GmbH, Berlin/Boston
Articles in the same Issue
- Frontmatter
- Reviews
- Electronic structure theory study of the reactivity and structural molecular properties of halo-substituted (F, Cl, Br) and heteroatom (N, O, S) doped cyclobutane
- Design of hydrogen supply chains under demand uncertainty – a case study of passenger transport in Germany
- Experimental investigation of ternary mixture of diclofenac sodium with pharmaceutical excipients
- Detection of cysteine-rich peptides in Tragia benthamii Baker (Euphorbiaceae) and in vivo antiinflammatory effect in a chick model
- Role of heteroatoms and substituents on the structure, reactivity, aromaticity, and absorption spectra of pyrene: a density functional theory study
- Contribution of the volatile components from fresh egg, adult female and male of Pestarella tyrrhena to odour production
Articles in the same Issue
- Frontmatter
- Reviews
- Electronic structure theory study of the reactivity and structural molecular properties of halo-substituted (F, Cl, Br) and heteroatom (N, O, S) doped cyclobutane
- Design of hydrogen supply chains under demand uncertainty – a case study of passenger transport in Germany
- Experimental investigation of ternary mixture of diclofenac sodium with pharmaceutical excipients
- Detection of cysteine-rich peptides in Tragia benthamii Baker (Euphorbiaceae) and in vivo antiinflammatory effect in a chick model
- Role of heteroatoms and substituents on the structure, reactivity, aromaticity, and absorption spectra of pyrene: a density functional theory study
- Contribution of the volatile components from fresh egg, adult female and male of Pestarella tyrrhena to odour production
