Synthesis of a Perfluorinated Phenoxyphosphorane and Conversion to Its Hexacoordinate Anions

Abstract

We report the synthesis and structuralc haracterization of an eutralP V Lewis acid, P(OC 6 F 5 ) 5 ,a nd salts containing the six-coordinate anions[ P(OC 6 F 5 ) 5 F] À and [P(OC 6 F 5 ) 6 ] À . The latter anion exhibits ar are example of F-p arene interactions in both the solid and the solution phase, which has been quantitativelys tudied by variable-temperature (VT) NMR spectroscopy.T he Lewis acid strength of P(OC 6 F 5 ) 5 has been assessed throughe xperimentalf luoridei on competi-tion experiments and quantum-chemical calculations of its fluoridei on affinity (FIA) and global electrophilicity index (GEI).O ur findings highlight the importanceo fc onsidering solvent effects in electrophilicity calculations, even when neutralL ewis acidsa re involved, and show ar are divergence betweenF IA and GEI trends. The coordinating abilities of the [P(OC 6 F 5 ) 6 ] À and [P(OC 6 F 5 ) 5 F] À anions towards the trityl cation, as ap rototypical electrophile,h ave been assessed.

High Lewis Acidity at Planar, Trivalent, and Neutral Bismuth Centers

“…To assess whether the significantly smaller and negatively charged fluoride ligand reveals different acidity trends compared to the neutral and larger ONMe 3 , we have calculated the FIA for the full set of Lewis acids studied here (Figure 7). Previous work has revealed some limitations of FIA values as indicators of absolute Lewis acidity when calculations have been performed in the gas phase (without a solvent model), 95 but relative Lewis acidity can be reasonably predicted through gas-phase calculations. 15,84 For consistency with the rest of the calculations in this study and other studies in this field, only the gas-phase FIA values are reported here.…”

An Extensive Set of Accurate Fluoride Ion Affinities for p‐Block Element Lewis Acids and Basic Design Principles for Strong Fluoride Ion Acceptors

“…A third flaw of the FIA transpires when it comes to the interpretation of solution‐phase experimental data. Since the fluoride ion binding reaction necessarily involves charged species, it is strongly affected by solvation energies – both for cationic and neutral Lewis acids . However, FIA have been computed commonly in vacuum only.…”

Tuning the Lewis Acidity of Neutral Silanes Using Perfluorinated Aryl‐ and Alkoxy Substituents

“…F : The title compound was synthesized according to an adapted procedure for LiOPh F given in the literature. [21] In this case 3.00 g p-heptafluorocresol (12.82 mmol, 1.00 equiv.) were dissolved in 50 ml hexane and 5.13 ml 2.5 m nBuLi solution in hexane (12.82 mmol, 1.00 equiv.)…”