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Phosphorus-31 contact shifts as a measure of weak ligand affinities. Interaction between alkali metal fluorenone radical anions and certain phosphorus(III or V) ligands

✍ Scribed by Constantinos G. Screttas; George A. Heropoulos; Barry R. Steele; Donald Bethell


Publisher
John Wiley and Sons
Year
1998
Tongue
English
Weight
199 KB
Volume
36
Category
Article
ISSN
0749-1581

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✦ Synopsis


The nuclear magnetic resonance shifts, induced to 31P in and by d obs , P h 3 P, (MeO) 3 P (MeO) 3 PO alkali metal Ñuorenone radical anions in tetrahydrofuran solutions were measured. These parameters, which depend signiÐcantly on the cation for a given ligand, and also on the ligand for a given cation, were used to extract the corresponding 31P contact shifts,

The latter parameters are proposed as a measure of the ligand affinity d c (M). of a given phosphorus compound for a particular alkali metal. Trimethyl phosphate exhibits the greatest affinity for the lithium cation. The magnitudes of imply some covalency between the cation and the radical anion and d c (M) the "paradoxÏ of a heavier alkali metal such as potassium being covalently bonded to Ñuorenone radical anion has been explained. The transferability of the reported ligand affinities of Li, Naand K`is discussed.