APPLICATIONS AND EVALUATIONS OF IGLO CHEMICAL-SHIFT CALCULATIONS FOR ORGANOLITHIUM COMPOUNDS

Journal article


Publication Details

Author(s): Bühl M, van Eikema Hommes N, Schleyer P, Fleischer U, Kutzelnigg W
Journal: Journal of the American Chemical Society
Publisher: American Chemical Society
Publication year: 1991
Volume: 113
Journal issue: 7
Pages range: 2459-2465
ISSN: 0002-7863


Abstract


The individual gauge for localized orbitals (IGLO) method has been applied to calculate the C-13 NMR shifts of numerous organolithium compounds. For the compounds existing as monomers in solution, the accord with experiment is satisfactory. The dependence of the calculated chemical shifts on aggregation and solvation was studied systematically for methyl-, vinyl-, and propynyllithium: these effects are shown to be most important for the unsaturated compounds but tend to cancel. For the aliphatic compounds, the effect of solvation and aggregation on delta-C-13 is smaller. Hence, even IGLO chemical shifts calculated for isolated saturated monomers give acceptable agreement with the experimental values for aggregated species. Calculated C-13 chemical shifts for unsaturated organolithium compounds can be related to the pi-electron density analogous to the Spiesecke-Schneider relationship. In some cases, IGLO calculations may be used to distinguish between structural possibilities; e.g., in benzyllithium the lithium cation is attached mainly to the benzylic and ipso carbons.



FAU Authors / FAU Editors

Schleyer, Paul Prof. Dr.
Naturwissenschaftliche Fakultät
van Eikema Hommes, Nico Dr.
Computer-Chemie-Centrum


How to cite

APA:
Bühl, M., van Eikema Hommes, N., Schleyer, P., Fleischer, U., & Kutzelnigg, W. (1991). APPLICATIONS AND EVALUATIONS OF IGLO CHEMICAL-SHIFT CALCULATIONS FOR ORGANOLITHIUM COMPOUNDS. Journal of the American Chemical Society, 113(7), 2459-2465. https://dx.doi.org/10.1021/ja00007a017

MLA:
Bühl, Michael, et al. "APPLICATIONS AND EVALUATIONS OF IGLO CHEMICAL-SHIFT CALCULATIONS FOR ORGANOLITHIUM COMPOUNDS." Journal of the American Chemical Society 113.7 (1991): 2459-2465.

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Last updated on 2018-19-04 at 03:17