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Steric effects in 31P NMR spectra: ‘Gamma’ shielding in aliphatic phosphorus compounds

✍ Scribed by Louis D. Quin; Joseph J. Breen

Publisher
John Wiley and Sons
Year
1973
Tongue
English
Weight
254 KB
Volume
5
Category
Article
ISSN
0749-1581

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✦ Synopsis

Abstract

An examination of published ^31^P NMR spectral data for aliphatic phosphorus compounds has revealed that chain lengthening and branching effects on the chemical shift can be interpreted in terms similar to those used for ^13^C and ^15^N shifts. For six families of phosphorus compounds, a β‐carbon substituent was shown to deshield phosphorus, while a γ‐carbon caused shielding. The effects are additive, and good agreement was obtained between ^31^P shifts calculated with the appropriate constants and the experimental values. Shielding by γ‐carbon is indicative of the operation of a steric influence on ^31^P chemical shifts, not heretofore articulated. The γ‐effect is also useful in explaining the unusually large shielding found in six‐membered cyclic phosphines.

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