Hexaphenyl-1,2-Diphosphonium Dication [Ph3P–PPh3]2+: Superacid, Superoxidant, or Super Reagent? DOI Creative Commons
Fabian Dankert,

Simon P. Muhm,

Chandan Nandi

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 24, 2025

The oxidation of triphenylphosphine by perfluorinated phenaziniumF aluminate in difluorobenzene affords hexaaryl-1,2-diphosphonium dialuminate 1. Dication 12+ is valence isoelectronic with elusive hexaphenylethane, where instead the formation a mixture trityl radical and Gomberg's dimer favored. Quantum-chemical calculations combination Raman/IR spectroscopies rationalize stability P-P bonded suggest, akin to halogens, facile homolytic as well heterolytic scission. Thus, serves surrogate both triphenylphosphorandiylium dication (Ph3P2+) monocation (Ph3P·+). Treating 1 dimethylaminopyridine (DMAP) or tBu3P replaces under bond Qualifying superoxidant (E vs Fc/Fc+ = +1.44 V), oxidizes trimethylphosphine. Based on halide abstraction experiments (-BF4, -PF6, -SbCl6, -SbF6) deoxygenation triethylphosphine oxide, triflate anions toluic acid, also features Lewis superacidity. controlled hydrolysis Hendrickson's reagent, which itself finds broad use dehydration agent. Formally, scission occurs diphenyldisulfide (PhSSPh) triple bonds benzo- acetonitrile. irradiation light cleaves homolytically generates transient cations, engage H-atom CH phosphoranylation.

Language: Английский

Hexaphenyl-1,2-Diphosphonium Dication [Ph3P–PPh3]2+: Superacid, Superoxidant, or Super Reagent? DOI Creative Commons
Fabian Dankert,

Simon P. Muhm,

Chandan Nandi

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 24, 2025

The oxidation of triphenylphosphine by perfluorinated phenaziniumF aluminate in difluorobenzene affords hexaaryl-1,2-diphosphonium dialuminate 1. Dication 12+ is valence isoelectronic with elusive hexaphenylethane, where instead the formation a mixture trityl radical and Gomberg's dimer favored. Quantum-chemical calculations combination Raman/IR spectroscopies rationalize stability P-P bonded suggest, akin to halogens, facile homolytic as well heterolytic scission. Thus, serves surrogate both triphenylphosphorandiylium dication (Ph3P2+) monocation (Ph3P·+). Treating 1 dimethylaminopyridine (DMAP) or tBu3P replaces under bond Qualifying superoxidant (E vs Fc/Fc+ = +1.44 V), oxidizes trimethylphosphine. Based on halide abstraction experiments (-BF4, -PF6, -SbCl6, -SbF6) deoxygenation triethylphosphine oxide, triflate anions toluic acid, also features Lewis superacidity. controlled hydrolysis Hendrickson's reagent, which itself finds broad use dehydration agent. Formally, scission occurs diphenyldisulfide (PhSSPh) triple bonds benzo- acetonitrile. irradiation light cleaves homolytically generates transient cations, engage H-atom CH phosphoranylation.

Language: Английский

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