1. bookVolume 5 (2012): Issue 2 (October 2012)
Journal Details
License
Format
Journal
eISSN
1339-3065
ISSN
1337-978X
First Published
10 Dec 2012
Publication timeframe
2 times per year
Languages
English
access type Open Access

Theoretical 1H(Se—H) NMR shifts in meta-substituted Ph—XH (X = O, S, Se)

Published Online: 14 Dec 2012
Volume & Issue: Volume 5 (2012) - Issue 2 (October 2012)
Page range: 159 - 163
Journal Details
License
Format
Journal
eISSN
1339-3065
ISSN
1337-978X
First Published
10 Dec 2012
Publication timeframe
2 times per year
Languages
English
Abstract

A systematic comparative theoretical study has been performed on a series of fourteen metasubstituted selenophenols. The optimal geometries were calculated using the density functional theory (DFT) and the Nuclear Magnetic Resonance parameters were computed by applying the Gauge Including Atomic Orbital (GIAO) method. The calculated NMR shifts were correlated with the Hammett constants. The obtained results were also compared with the theoretical data obtained for thiophenols and phenols. Our results indicate the linear dependence between the gas-phase NMR shifts and Hammett constants. However, the presence of large selenium atoms is able to suppress significantly the substituent effect in meta position. Therefore six substituents (Me, OH, MeCO, COOMe, COOEt and CF3 groups) were excluded from the data evaluation. Correlations with the fundamental stretching vibration frequencies of the mode with the dominant Se-H vibration have not been found.

Keywords

Becke AD (1993) J. Chem. Phys. 98: 5648-5652.Search in Google Scholar

Binkley JS, Pople JA, Hehre WJ (1980) J. Am. Chem. Soc. 102: 939-947.Search in Google Scholar

Ditchfield R (1974) Mol. Phys. 27: 789.Search in Google Scholar

Duddeck H (1995) Prog. in NMR Spectroscopy 27: 1-323.10.1016/0079-6565(94)00005-FSearch in Google Scholar

Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery JA, Jr., Vreven T, Kudin KN, Burant JC, Millam JM, Iyengar SS, Tomasi J, Barone V, Mennucci B, Cosi M, Scalmani G, Rega N, Petersson GA, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegava J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox JE, Hratchian HP, Cross JB, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Ayala PY, Morokuma K, Voth GA, Salvador P, Dannenberg JJ, Zakrzewski VG, Dapprich S, Daniels AD, Strain M-C, Farkas O, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Ortiz JV, Cui Q, Baboul AG, Clifford S, Cioslowski J, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nakaryakkara A, Chalacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Gonzales C, Pople JA; GAUSSIAN 03. Revision A.1. Pittsburg. Pa. (2003).Search in Google Scholar

Hansch C, Leo A, Taft RW (1991) Chem. Rev. 91: 165.Search in Google Scholar

Klein E, Lukeš V (2006) J. Mol. Struct. (Theochem) 767: 43-50.10.1016/j.theochem.2006.04.017Search in Google Scholar

Rimarčik J, Lukeš V, Klein E, Rottmannova L (2011) Comput. Theor. Chem. 967: 273-283.Search in Google Scholar

Lalezari I, Sharghi N (1964) Spectrochim. 20: 237.Search in Google Scholar

Leeck DT, Li R, Chyall LJ, Kenttamaa HI (1996) J. Phys. Chem. 100: 6608-6611.Search in Google Scholar

Merijanian A. Zingaro RA. Sagan LS. Irgolic KJ (1969) Spectrochim. Acta 25: 1160.10.1016/0584-8539(69)80115-7Search in Google Scholar

Newcomb M, Varick TR, Ha C, Manek MB, Yue XJ (1992) J. Am. Chem. Soc. 114: 8158.Search in Google Scholar

Smith RL, Chyall LJ, Stirk KM, Kenttamaa HI (1993) Org. Mass Spectrom. 28: 1623.Search in Google Scholar

Yan SG, Zhang AL, Zhou K (1995) Spectrochim. Acta A 51: 2421-2423.10.1016/0584-8539(95)01463-2Search in Google Scholar

Recommended articles from Trend MD

Plan your remote conference with Sciendo