Computed NMR shielding increments over unsaturated five-membered ring heterocyclic compounds as a measure of aromaticity
作者： Ned H. Martin , Jimmy E. Rowe , Eddie LaReece Pittman
DOI: 10.1016/J.JMGM.2009.01.002
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摘要: The GIAO-HF method within Gaussian 03 was used to calculate the isotropic shielding value of proximal hydrogen a diatomic probe at various distances (2.5 A, 3.0 A and 4.0 A) above plane 15 conjugated five-membered ring heterocyclic compounds: pyrrole, furan, thiophene, phosphole their 2- 3-nitrogen analogs. Subtraction by itself from each these values gave increment (Deltasigma) for position. Plotting Deltasigma against Cartesian coordinates position allowed determination computed through-space surfaces compounds. Substantial observed center ring, as expected aromatic magnitude 2.5 (Deltasigma(2.5)) correlated reasonably well with other established methods assessing aromaticity, including geometric (HOMA, harmonic oscillator model aromaticity), energetic (ASE, stabilization energy), magnetic (NICS, nucleus-independent chemical shift) criteria.
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sci-hub.se 参考文章(33)
D. H. Rouvray, Concepts in Chemistry: A Contemporary Challenge ,(1996)
István Hargittai, Magdolna Hargittai, Advances in molecular structure research JAI Press Inc.. ,(1995)
Sabrina Klod, Erich Kleinpeter, Ab initio calculation of the anisotropy effect of multiple bonds and the ring current effect of arenes—application in conformational and configurational analysis Journal of The Chemical Society-perkin Transactions 1. pp. 1893- 1898 ,(2001) , 10.1039/B009809O
T. M. KRYGOWSKI, M. CYRANSKI, Aromatic Character of Carbocyclic π-Electron Systems Deduced from Molecular Geometry ChemInform. ,vol. 28, ,(2010) , 10.1002/CHIN.199742352
Remi Chauvin, Explicit periodic trend of van der Waals radii The Journal of Physical Chemistry. ,vol. 96, pp. 9194- 9197 ,(1992) , 10.1021/J100202A023
Ned H. Martin, David M. Loveless, Kristin L. Main, Dustin C. Wade, Computation of through-space NMR shielding effects by small-ring aromatic and antiaromatic hydrocarbons. Journal of Molecular Graphics & Modelling. ,vol. 25, pp. 389- 395 ,(2006) , 10.1016/J.JMGM.2006.02.006
Tadeusz Marek Krygowski, Crystallographic studies of inter- and intramolecular interactions reflected in aromatic character of .pi.-electron systems Journal of Chemical Information and Computer Sciences. ,vol. 33, pp. 70- 78 ,(1993) , 10.1021/CI00011A011
W. H. Flygare, Magnetic interactions in molecules and an analysis of molecular electronic charge distribution from magnetic parameters Chemical Reviews. ,vol. 74, pp. 653- 687 ,(1974) , 10.1021/CR60292A003
Erich Kleinpeter, Sabrina Klod, Ab initio calculation of the anisotropic/ring current effects of amino acid residues to locate the position of substrates in the binding site of enzymes Journal of Molecular Structure. ,vol. 704, pp. 79- 82 ,(2004) , 10.1016/J.MOLSTRUC.2003.12.062
Ned H. Martin, Justin D. Brown, Kimberly H. Nance, Henry F. Schaefer, Paul v. R. Schleyer, Zhi-Xiang Wang, H. Lee Woodcock, Analysis of the origin of through-space proton NMR deshielding by selected organic functional groups. Organic Letters. ,vol. 3, pp. 3823- 3826 ,(2001) , 10.1021/OL016500U