Multinuclear nuclear magnetic resonance study of the interaction of some phosphorus(V) compounds with inorganic acids. The protonating abilities of HNO3, MeSO3H, and HPO2F2 towards the phosphoryl group
- 1 January 1985
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 4,p. 865-866
- https://doi.org/10.1039/dt9850000865
Abstract
The influence of protonation upon 31P and 17O n.m.r. parameters of the phosphoryl compounds POCl3 and HPO2F2 has been investigated. For POCl3, δ(17O) and 1J(P–O) decrease whereas δ(31P) increases with increasing protonation of the phosphoryl group. For HPO2F2 the changes in δ(17O) and δ(31P) were less informative although 1J(P–F) appears to increase smoothly with increasing protonation. The same trend in 1J(P–F) is observed for solutions of Na2PO3F in some inorganic acids (MeSO3H, CF3CO2H, HNO3, HSO3Cl, and 25 oleum). The POCl3 results indicate that the ability of HNO3 to protonate the phosphoryl group is significantly greater than would be anticipated on the basis of Hammett acidity-function measurements, whereas the protonating ability of MeSO3H is as anticipated on the basis of its Hammett function and that of HPO2F2 is lower than those of HNO3 and MeSO3H, comparable with that of liquid HCl. The values of δ(31P) of POBr3 in HNO3, MeSO3H, and HPO2F2 are in agreement with the above conclusions.Keywords
This publication has 0 references indexed in Scilit: