Solvent effects on the boron–fluorine coupling constant and on fluorine exchange in the tetrafluoroborate anion
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Abstract
The 11 B— 19 F spin–spin coupling constant in AgBF 4 is shown to have an opposite sign in water from that found in a number of organic solvents. Application of the hypothesis of Bell and Danyluk indicates that it has a positive sign in water. Evidence is presented for association, probably in the form of solvent-separated ion pairs, in aqueous LiBF 4 and NaBF 4 solutions, and for the formation of more tightly bound ion pairs in solvents of lower dielectric constant. In contrast, there apparently is no solute association in AgBF 4 solutions in water, DMSO, DMF, or acetonitrile. The pronounced changes observed in the 11 B— 19 F coupling constant support the postulate that its small size is a result of near cancellation of large opposing terms.The collapse of the 10 B— 11 B isotope shift at high temperatures in the 19 F spectra of solutions of AgBF 4 in acetonitrile and in acetone provides evidence for exchange of fluorine among boron atoms; a mechanism is proposed for this process.
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