[P(4)H](+)[Al(OTeF(5))(4)](–): protonation of white phosphorus with the Brønsted superacid H[Al(OTeF(5))(4)]((solv))

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.