Electron Delocalization in Electron-Deficient Alkenes and Push-Pull Alkenes
Abstract
We have studied pi electron delocalization in electron- deficient alkenes and push- pull alkenes by means of natural bond orbital analysis at the B3LYP/6-311+ G(d,p) level. The study revealed that the rarely mentioned pi electron donation from an electron-accepting group (Acc) toward the C=C double bond in push-pull alkenes and electron-deficient alkenes can provide up to 10% of total pi electron stabilizing energy of a push-pull system and as much as 45% in a strongly electron-deficient tetracyanoethene. The Acc - gt C= C bond pi electron donation is more intense in s-trans than in s-cis conformational arrangement, but is less dependent on Z/E isomerism in push-pull alkenes, being slightly more pronounced in Z isomers. Among different Acc substituents, CN and COO-groups contribute the largest percent of stabilizing energy and NO2 the smallest. Increase in the number of Acc groups increases percentage contribution of Acc - gt C= C bond p electron delocalization to a system stabilizat...ion. A difference in pi*(C=C) orbital occupancy between isomers can be related with their chemical reactivity.
Keywords:
density functional theory / electron-deficient alkene / electron delocalization / electronic structure / push-pull alkeneSource:
CHEMISTRYSELECT, 2017, 2, 1, 42-50Publisher:
- 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:
- Supplementary material: http://cherry.chem.bg.ac.rs/handle/123456789/3112
DOI: 10.1002/slct.201601661
ISSN: 2365-6549
WoS: 000395434600006
Scopus: 2-s2.0-85037061816
Collections
Institution/Community
Hemijski fakultet / Faculty of ChemistryTY - JOUR AU - Džambaski, Zdravko AU - Baranac-Stojanović, Marija PY - 2017 UR - https://cherry.chem.bg.ac.rs/handle/123456789/2425 AB - We have studied pi electron delocalization in electron- deficient alkenes and push- pull alkenes by means of natural bond orbital analysis at the B3LYP/6-311+ G(d,p) level. The study revealed that the rarely mentioned pi electron donation from an electron-accepting group (Acc) toward the C=C double bond in push-pull alkenes and electron-deficient alkenes can provide up to 10% of total pi electron stabilizing energy of a push-pull system and as much as 45% in a strongly electron-deficient tetracyanoethene. The Acc - gt C= C bond pi electron donation is more intense in s-trans than in s-cis conformational arrangement, but is less dependent on Z/E isomerism in push-pull alkenes, being slightly more pronounced in Z isomers. Among different Acc substituents, CN and COO-groups contribute the largest percent of stabilizing energy and NO2 the smallest. Increase in the number of Acc groups increases percentage contribution of Acc - gt C= C bond p electron delocalization to a system stabilization. A difference in pi*(C=C) orbital occupancy between isomers can be related with their chemical reactivity. PB - Wiley-V C H Verlag Gmbh, Weinheim T2 - CHEMISTRYSELECT T1 - Electron Delocalization in Electron-Deficient Alkenes and Push-Pull Alkenes VL - 2 IS - 1 SP - 42 EP - 50 DO - 10.1002/slct.201601661 ER -
@article{ author = "Džambaski, Zdravko and Baranac-Stojanović, Marija", year = "2017", abstract = "We have studied pi electron delocalization in electron- deficient alkenes and push- pull alkenes by means of natural bond orbital analysis at the B3LYP/6-311+ G(d,p) level. The study revealed that the rarely mentioned pi electron donation from an electron-accepting group (Acc) toward the C=C double bond in push-pull alkenes and electron-deficient alkenes can provide up to 10% of total pi electron stabilizing energy of a push-pull system and as much as 45% in a strongly electron-deficient tetracyanoethene. The Acc - gt C= C bond pi electron donation is more intense in s-trans than in s-cis conformational arrangement, but is less dependent on Z/E isomerism in push-pull alkenes, being slightly more pronounced in Z isomers. Among different Acc substituents, CN and COO-groups contribute the largest percent of stabilizing energy and NO2 the smallest. Increase in the number of Acc groups increases percentage contribution of Acc - gt C= C bond p electron delocalization to a system stabilization. A difference in pi*(C=C) orbital occupancy between isomers can be related with their chemical reactivity.", publisher = "Wiley-V C H Verlag Gmbh, Weinheim", journal = "CHEMISTRYSELECT", title = "Electron Delocalization in Electron-Deficient Alkenes and Push-Pull Alkenes", volume = "2", number = "1", pages = "42-50", doi = "10.1002/slct.201601661" }
Džambaski, Z.,& Baranac-Stojanović, M.. (2017). Electron Delocalization in Electron-Deficient Alkenes and Push-Pull Alkenes. in CHEMISTRYSELECT Wiley-V C H Verlag Gmbh, Weinheim., 2(1), 42-50. https://doi.org/10.1002/slct.201601661
Džambaski Z, Baranac-Stojanović M. Electron Delocalization in Electron-Deficient Alkenes and Push-Pull Alkenes. in CHEMISTRYSELECT. 2017;2(1):42-50. doi:10.1002/slct.201601661 .
Džambaski, Zdravko, Baranac-Stojanović, Marija, "Electron Delocalization in Electron-Deficient Alkenes and Push-Pull Alkenes" in CHEMISTRYSELECT, 2, no. 1 (2017):42-50, https://doi.org/10.1002/slct.201601661 . .
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Supplementary data for article: Džambaski, Z.; Baranac-Stojanović, M. Electron Delocalization in Electron-Deficient Alkenes and Push-Pull Alkenes. ChemistrySelect 2017, 2 (1), 42–50. https://doi.org/10.1002/slct.201601661
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