A Tautomeric λ 3 /λ 5 -Phosphane Pair and Its Ambiphilic Reactivity.

The central phosphorus atom of a novel hydroxyl-functionalized triarylphosphane was shown to reversibly insert into one of the molecule's O-H bonds, which forms the basis for a tautomeric λ3 /λ5 -phosphane equilibrium. For the first time, this equilibrium was detected for a λ3 -triarylphosphane and the underlying dynamic process was elucidated by NMR spectroscopy. On the basis of reactivity studies, a nucleophilic character was assigned to the minor species present in solution, the λ3 -phosphane. Upon methylation, for example, the λ3 -form was selectively removed from the equilibrium and converted to the corresponding phosphonium salt. However, upon generation of an alkoxide via proton abstraction, the electrophilic character of the λ5 -phosphane in the equilibrium became evident since the alkoxide was found to attack the molecule's phosphorus atom. This intramolecular reaction led to the selective formation of a new anionic λ6 -hydridospirophosphane.