Electrostatic Properties of N-Heterocyclic Carbenes Obtained by Experimental Charge-Density Analysis of Two Selenium Adducts
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2016
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© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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High-resolution X-ray diffraction data and Hansen-Coppens multipole formalism have been used to obtain the charge density distribution in two selenium adducts with the N-heterocyclic carbenes 1,3-dimesitylimidazolidin-2-ylidene (1) and 1,3-dimesityl-4,5-dioxoimidazolidin-2-ylidene (2). Application of Baders quantum theory of atoms in molecules and calculation of the atomic charges by integration of the experimental electron density over the atomic basins showed that the main electrostatic difference between the Se adducts is in the significantly different accumulation of electron density in their C-(carbene)-Se fragments (-0.10 vs. + 0.30 e in 1 and 2). Deformation electron density features along the C-Se bond and topological values at the bond critical point indicate that this bond has pi character in both compounds but it is more pronounced in the case of 2. This is in agreement with stronger C-N bonds and a larger N-C-N angle in 1. The experimental charge density distribution also c...learly indicates the important role of the N-mesityl substituent as an electron-donating group, which increases the electron density in the imidazole ring thus contributing to the electronic stabilization of the carbene C atom. Because the N-mesityl substituents donate similar amounts of electron density in both molecules (0.75 and 0.64 e in 1 and 2), it was concluded that the decisively different electronic properties of the two NHCs have to be attributed to their different backbone structures.
Кључне речи:
Carbenes / Selenium / Electron density / X-ray diffractionИзвор:
European Journal of Inorganic Chemistry, 2016, 21, 3389-3395Финансирање / пројекти:
- Дизајнирање, синтеза, карактеризација и процена практичне примене координационих и органометалних једињења (RS-MESTD-Basic Research (BR or ON)-172014)
- Рационални дизајн и синтеза биолошки активних и координационих једињења и функционалних материјала, релевантних у (био)нанотехнологији (RS-MESTD-Basic Research (BR or ON)-172035)
DOI: 10.1002/ejic.201600292
ISSN: 1434-1948; 1099-0682
WoS: 000383607000006
Scopus: 2-s2.0-84977569074
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Институција/група
VinčaTY - JOUR AU - Buhl, Hannes AU - Verlinden, Kathrin AU - Ganter, Christian AU - Novaković, Slađana B. AU - Bogdanović, Goran A. PY - 2016 UR - https://vinar.vin.bg.ac.rs/handle/123456789/1248 AB - High-resolution X-ray diffraction data and Hansen-Coppens multipole formalism have been used to obtain the charge density distribution in two selenium adducts with the N-heterocyclic carbenes 1,3-dimesitylimidazolidin-2-ylidene (1) and 1,3-dimesityl-4,5-dioxoimidazolidin-2-ylidene (2). Application of Baders quantum theory of atoms in molecules and calculation of the atomic charges by integration of the experimental electron density over the atomic basins showed that the main electrostatic difference between the Se adducts is in the significantly different accumulation of electron density in their C-(carbene)-Se fragments (-0.10 vs. + 0.30 e in 1 and 2). Deformation electron density features along the C-Se bond and topological values at the bond critical point indicate that this bond has pi character in both compounds but it is more pronounced in the case of 2. This is in agreement with stronger C-N bonds and a larger N-C-N angle in 1. The experimental charge density distribution also clearly indicates the important role of the N-mesityl substituent as an electron-donating group, which increases the electron density in the imidazole ring thus contributing to the electronic stabilization of the carbene C atom. Because the N-mesityl substituents donate similar amounts of electron density in both molecules (0.75 and 0.64 e in 1 and 2), it was concluded that the decisively different electronic properties of the two NHCs have to be attributed to their different backbone structures. T2 - European Journal of Inorganic Chemistry T1 - Electrostatic Properties of N-Heterocyclic Carbenes Obtained by Experimental Charge-Density Analysis of Two Selenium Adducts IS - 21 SP - 3389 EP - 3395 DO - 10.1002/ejic.201600292 ER -
@article{ author = "Buhl, Hannes and Verlinden, Kathrin and Ganter, Christian and Novaković, Slađana B. and Bogdanović, Goran A.", year = "2016", abstract = "High-resolution X-ray diffraction data and Hansen-Coppens multipole formalism have been used to obtain the charge density distribution in two selenium adducts with the N-heterocyclic carbenes 1,3-dimesitylimidazolidin-2-ylidene (1) and 1,3-dimesityl-4,5-dioxoimidazolidin-2-ylidene (2). Application of Baders quantum theory of atoms in molecules and calculation of the atomic charges by integration of the experimental electron density over the atomic basins showed that the main electrostatic difference between the Se adducts is in the significantly different accumulation of electron density in their C-(carbene)-Se fragments (-0.10 vs. + 0.30 e in 1 and 2). Deformation electron density features along the C-Se bond and topological values at the bond critical point indicate that this bond has pi character in both compounds but it is more pronounced in the case of 2. This is in agreement with stronger C-N bonds and a larger N-C-N angle in 1. The experimental charge density distribution also clearly indicates the important role of the N-mesityl substituent as an electron-donating group, which increases the electron density in the imidazole ring thus contributing to the electronic stabilization of the carbene C atom. Because the N-mesityl substituents donate similar amounts of electron density in both molecules (0.75 and 0.64 e in 1 and 2), it was concluded that the decisively different electronic properties of the two NHCs have to be attributed to their different backbone structures.", journal = "European Journal of Inorganic Chemistry", title = "Electrostatic Properties of N-Heterocyclic Carbenes Obtained by Experimental Charge-Density Analysis of Two Selenium Adducts", number = "21", pages = "3389-3395", doi = "10.1002/ejic.201600292" }
Buhl, H., Verlinden, K., Ganter, C., Novaković, S. B.,& Bogdanović, G. A.. (2016). Electrostatic Properties of N-Heterocyclic Carbenes Obtained by Experimental Charge-Density Analysis of Two Selenium Adducts. in European Journal of Inorganic Chemistry(21), 3389-3395. https://doi.org/10.1002/ejic.201600292
Buhl H, Verlinden K, Ganter C, Novaković SB, Bogdanović GA. Electrostatic Properties of N-Heterocyclic Carbenes Obtained by Experimental Charge-Density Analysis of Two Selenium Adducts. in European Journal of Inorganic Chemistry. 2016;(21):3389-3395. doi:10.1002/ejic.201600292 .
Buhl, Hannes, Verlinden, Kathrin, Ganter, Christian, Novaković, Slađana B., Bogdanović, Goran A., "Electrostatic Properties of N-Heterocyclic Carbenes Obtained by Experimental Charge-Density Analysis of Two Selenium Adducts" in European Journal of Inorganic Chemistry, no. 21 (2016):3389-3395, https://doi.org/10.1002/ejic.201600292 . .