Dynamic activation of alcohols by an electrophilic phosphinine

A bis(trifluoromethyl)-substituted phosphinine undergoes reversible oxidative addition of primary and secondary alcohols at the low-coordinate phosphorus(III) atom. This unprecedented reactivity contrasts the general inertness of uncoordinated phosphinines toward protic substrates and provides a rare example of reversible alcohol activation mediated by a main-group element compound. DFT calculations suggest that a hydrogen-bonded methanol network enables the transformation, offering a new concept for dynamic E-H bond activation by electrophilic, aromatic phosphorus heterocycles.