An NMR shielding model for protons above the plane of a carbonyl group

• Published in: Journal of molecular graphics & modelling 2003-11, Vol.22 (2), p.127-131
• Main Authors: Martin, Ned H., Allen, Noah W., Brown, Justin D., Kmiec, David M., Vo, Luong
• Format: Article
• Language: English
• Subjects: Anisotropy; Carbon - chemistry; Carbonyl group; Formaldehyde; GIAO-HF; Isotropic shielding value; Magnetic anisotropy; Magnetic Resonance Spectroscopy - methods; Molecular Structure; NMR; Protons
• ISSN: 1093-3263; 1873-4243
• DOI: 10.1016/S1093-3263(03)00152-9

Covalently bonded hydrogen nuclei located over the plane of a carbonyl group in a strong magnetic field experience magnetic shielding (or deshielding) that results from the combined effect of the magnetic anisotropy of the carbon–oxygen double bond and various other intramolecular shielding effects. GIAO-HF in Gaussian 98 was employed to calculate isotropic shielding values and to predict the net proton NMR shielding increment for a simple model system: the proximate proton of methane held in various positions over formaldehyde. The net shielding increments of the proximate proton of methane, plotted against its Cartesian coordinates relative to the center of the carbon–oxygen double bond, led to the development of a single empirical equation for predicting the NMR shielding experienced by a covalently bonded proton over the plane of a carbonyl group. The predictive capability of this equation has been validated by calculating the shielding increments of protons over the plane of a carbonyl group in known structures, using this as a correction to the chemical shift estimated by subtituent effects and comparing the result to experimentally observed chemical shifts. Shielding is predicted by this equation for protons located in the region from over the center of the carbon–oxygen double bond to beyond the carbon atom; deshielding is predicted for protons located above and beyond the oxygen atom. This prediction differs from those made by the long-held “shielding cone” model found in nearly every textbook on NMR, but is consistent with experimental observations. The algorithm for predicting the shielding increment for a proton over a carbonyl group can be used in a spreadsheet or incorporated into software that estimates chemical shifts using additive substituent constants or a database of structures. Its use can improve the accuracy of the estimated chemical shift of a proton in the vicinity of a carbon–oxygen double bond, and thus assist in spectral assignments and in correct structure determination.