DFT-GIAO and DFT-NBO studies of the origin of 19F NMR shielding effects in alkyl fluorides
Electron delocalization into the local environment of the fluorine nucleus in the anti (1) and syn (2) epimers of 7-norbornenyl fluoride, 7-fluoronorbornane (3), 7-fluoronobornadiene (4) and the equatorial and axial epimers of cyclohexyl fluoride (5 and 6, respectively) were studied using the natura...
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1999
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| LEADER | 08372caa a22009977a 4500 | ||
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| 001 | PAPER-2677 | ||
| 003 | AR-BaUEN | ||
| 005 | 20250204093051.0 | ||
| 008 | 190411s1999 xx ||||fo|||| 00| 0 eng|d | ||
| 024 | 7 | |2 scopus |a 2-s2.0-0033084268 | |
| 030 | |a MRCHE | ||
| 040 | |a Scopus |b spa |c AR-BaUEN |d AR-BaUEN | ||
| 100 | 1 | |a Adcock, W. | |
| 245 | 1 | 0 | |a DFT-GIAO and DFT-NBO studies of the origin of 19F NMR shielding effects in alkyl fluorides |
| 260 | |c 1999 | ||
| 270 | 1 | 0 | |m Contreras, R.H.; Departamento de Física, Fac. de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pabellón 1, (1428) Buenos Aires, Argentina |
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| 504 | |a De Kowalewski, D.G., Kowalewski, V.J., Contreras, R.H., Diez, E., Esteban, A.L., (1998) Magn. Reson. Chem., 36, p. 336 | ||
| 506 | |2 openaire |e Política editorial | ||
| 520 | 3 | |a Electron delocalization into the local environment of the fluorine nucleus in the anti (1) and syn (2) epimers of 7-norbornenyl fluoride, 7-fluoronorbornane (3), 7-fluoronobornadiene (4) and the equatorial and axial epimers of cyclohexyl fluoride (5 and 6, respectively) were studied using the natural bond orbital (NBO) approach. The level of theory, B3LYP/6-311G**, was chosen in such a way that the GIAO-calculated 19F magnetic shielding constants in all these compounds were in very good agreement with experimental values. The large 19F deshielding effects known experimentally in 1 and 4 with respect to 2 and 3 are rationalized in terms of differences in such electron delocalizations. The main contribution is that corresponding to the π → (C-F)* interaction, which is only efficient for an anti orientation of the C-F bond and the vinyl moiety. 19F and 13C NMR spectra of 5 and 6 were also measured because some ambiguity was detected in the literature. Despite the large calculated charge donation to the fluorine environment in 6, its 19F resonance appears upfield from that in 5. This trend is rationalized as originating in γ effects of the C-Hax bonds of the kind which have been invoked to explain 17O chemical shift trends in different cyclohexanols and their respective ethers. Electron delocalization effects on 1J(C,F) and 2J(C,F) couplings are also discussed. Copyright © 1999 John Wiley & Sons, Ltd. |l eng | |
| 593 | |a Department of Chemistry, Flinders Univ. of South Australia, Adelaide, SA 5001, Australia | ||
| 593 | |a Departamento de Física, Fac. de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pabellón 1, (1428) Buenos Aires, Argentina | ||
| 690 | 1 | 0 | |a 7-NORBORNENYL FLUORIDES |
| 690 | 1 | 0 | |a 19F CHEMICAL SHIFTS |
| 690 | 1 | 0 | |a 19F NMR |
| 690 | 1 | 0 | |a 1J(C,F)F AND 2J(C,F) COUPLINGS |
| 690 | 1 | 0 | |a CYCLOHEXYL FLUORIDES |
| 690 | 1 | 0 | |a DFT-GIAO |
| 690 | 1 | 0 | |a DFT-NBO |
| 690 | 1 | 0 | |a NMR |
| 700 | 1 | |a Lünsmann, D. | |
| 700 | 1 | |a Peralta, J.E. | |
| 700 | 1 | |a Contreras, Rubén Horacio | |
| 773 | 0 | |d 1999 |g v. 37 |h pp. 167-172 |k n. 3 |p Magn. Reson. Chem. |x 07491581 |w (AR-BaUEN)CENRE-972 |t Magnetic Resonance in Chemistry | |
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| 856 | 4 | 0 | |u https://hdl.handle.net/20.500.12110/paper_07491581_v37_n3_p167_Adcock |y Handle |
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