INTERPRETATION OF THE FLUORINE CHEMICAL SHIFT OF ClF

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1964

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Ohio State University

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Abstract

The chemical shift of $F^{19}$ in gaseous chlorine $mono-fluoride^{1}$ is about 875 ppm upfield from $F_{2}$

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or about 200 ppm above the estimated shift for the free ion, $F^{-}$. This represents a striking discrepancy with simple fluorine chemical shift theories, which generally predict all fluorine resonance shifts to be paramagnetic relative to $F^{-}$. The CIF anomaly can be accounted for satisfactorily as resulting from the valence-shell $\pi^{\ast} \rightarrow \sigma^{\ast}$ excitation, which corresponds to electron circulation in opposite senses on the two atoms.
Author Institution: Department of Chemistry, University of Wisconsin

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