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A sustainable transformation of white phosphorus (P 4 ) into chemicals of higher value is one of the key aspects in modern phosphorus research. Even though the chemistry of P 4 has been investigated for many decades, its chemical reactivity towards the simplest electrophile, the proton, is still virtually unknown. Based on quantum-chemical predictions, we report for the first time the successful protonation of P 4 by the Brønsted acid H[Al(OTeF 5 ) 4 ] (solv) . Our spectroscopic results are in agreement with acid-mediated activation of P 4 under protonation of an edge of the P 4 -tetrahedron and formation of a three-center two-electron P-H-P bond. These investigations are of fundamental interest as they permit the activation of P 4 with the simplest electrophile as a new prototype reaction for this molecule.

chemical science

[P4H]+[Al(OTeF5)4]−: protonation of white phosphorus with the Brønsted superacid H[Al(OTeF5)4](solv)