4-Electron B-N Monocycles: Stability and (Anti)aromaticity
Abstract
This is a theoretical (DFT) study of the impact of electronic structural changes, induced by B-N/C-C isosterism, on two basic properties of 4-electron antiaromatic system, that is, stability and antiaromaticity. The main driving force for the nonplanarity of B2N2 rings is electrostatic energy, and that for a ring with one B-N unit is the relief of Pauli repulsion. The charge-separation instability, inherent for a 1,3-B,N relationship, turns the ground state of the BCNC system to an aromatic triplet, which is less stable than the isomeric BNCC system, mostly because of larger Pauli interactions. The alternating BNBN connectivity is favoured primarily by orbital interaction energy and, secondarily, by better electrostatic attraction. The C-C B-N substitution weakens the antiaromatic character, except that for a 1,3-B,N relationship, which results in increased antiaromaticity in the closed-shell state relative to that of cyclobutadiene.
Keywords:
Aromaticity / Bond theory / Conjugation / Density functional calculations / HeterocyclesSource:
European Journal of Organic Chemistry, 2017, 34, 5163-5169Publisher:
- Wiley-V C H Verlag Gmbh, Weinheim
Funding / projects:
- Experimental and theoretical study of reactivity and biological activity of stereodefined thiazolidines and their synthetic analogues (RS-MESTD-Basic Research (BR or ON)-172020)
Note:
- This is the peer-reviewed version of the following article: Baranac-Stojanović, M. 4-Electron B-N Monocycles: Stability and (Anti)Aromaticity. European Journal of Organic Chemistry 2017, No. 34, 5163–5169. https://doi.org/10.1002/ejoc.201700959
Collections
Institution/Community
Hemijski fakultet / Faculty of ChemistryTY - JOUR AU - Baranac-Stojanović, Marija PY - 2017 UR - https://cherry.chem.bg.ac.rs/handle/123456789/3825 AB - This is a theoretical (DFT) study of the impact of electronic structural changes, induced by B-N/C-C isosterism, on two basic properties of 4-electron antiaromatic system, that is, stability and antiaromaticity. The main driving force for the nonplanarity of B2N2 rings is electrostatic energy, and that for a ring with one B-N unit is the relief of Pauli repulsion. The charge-separation instability, inherent for a 1,3-B,N relationship, turns the ground state of the BCNC system to an aromatic triplet, which is less stable than the isomeric BNCC system, mostly because of larger Pauli interactions. The alternating BNBN connectivity is favoured primarily by orbital interaction energy and, secondarily, by better electrostatic attraction. The C-C B-N substitution weakens the antiaromatic character, except that for a 1,3-B,N relationship, which results in increased antiaromaticity in the closed-shell state relative to that of cyclobutadiene. PB - Wiley-V C H Verlag Gmbh, Weinheim T2 - European Journal of Organic Chemistry T1 - 4-Electron B-N Monocycles: Stability and (Anti)aromaticity IS - 34 SP - 5163 EP - 5169 UR - https://hdl.handle.net/21.15107/rcub_cherry_3825 ER -
@article{ author = "Baranac-Stojanović, Marija", year = "2017", abstract = "This is a theoretical (DFT) study of the impact of electronic structural changes, induced by B-N/C-C isosterism, on two basic properties of 4-electron antiaromatic system, that is, stability and antiaromaticity. The main driving force for the nonplanarity of B2N2 rings is electrostatic energy, and that for a ring with one B-N unit is the relief of Pauli repulsion. The charge-separation instability, inherent for a 1,3-B,N relationship, turns the ground state of the BCNC system to an aromatic triplet, which is less stable than the isomeric BNCC system, mostly because of larger Pauli interactions. The alternating BNBN connectivity is favoured primarily by orbital interaction energy and, secondarily, by better electrostatic attraction. The C-C B-N substitution weakens the antiaromatic character, except that for a 1,3-B,N relationship, which results in increased antiaromaticity in the closed-shell state relative to that of cyclobutadiene.", publisher = "Wiley-V C H Verlag Gmbh, Weinheim", journal = "European Journal of Organic Chemistry", title = "4-Electron B-N Monocycles: Stability and (Anti)aromaticity", number = "34", pages = "5163-5169", url = "https://hdl.handle.net/21.15107/rcub_cherry_3825" }
Baranac-Stojanović, M.. (2017). 4-Electron B-N Monocycles: Stability and (Anti)aromaticity. in European Journal of Organic Chemistry Wiley-V C H Verlag Gmbh, Weinheim.(34), 5163-5169. https://hdl.handle.net/21.15107/rcub_cherry_3825
Baranac-Stojanović M. 4-Electron B-N Monocycles: Stability and (Anti)aromaticity. in European Journal of Organic Chemistry. 2017;(34):5163-5169. https://hdl.handle.net/21.15107/rcub_cherry_3825 .
Baranac-Stojanović, Marija, "4-Electron B-N Monocycles: Stability and (Anti)aromaticity" in European Journal of Organic Chemistry, no. 34 (2017):5163-5169, https://hdl.handle.net/21.15107/rcub_cherry_3825 .