Abstract
AbstractAn examination of published 31P 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 13C and 15N 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 31P shifts calculated with the appropriate constants and the experimental values. Shielding by γ‐carbon is indicative of the operation of a steric influence on 31P 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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