Highly electrophilic, 16-electron [Ru(P(OMe)(OH)(2))(dppe)(2)](2+) complex turns H(2)(g) into a strong acid and splits a Si-H bond heterolytically. Synthesis and structure of the novel phosphorous acid complex [Ru(P(OH)(3))(dppe)(2)](2+).

The highly electrophilic, 16-electron, coordinatively unsaturated [Ru(P(OMe)(OH)(2))(dppe)(2)]OTf complex brings about the heterolytic activation of H(2)(g) and spontaneously generates HOTf. In addition, trans-Ru(H)(P(OMe)(OH)(2))(dppe)(2) and an unprecedented example of a phosphorous acid complex, Ru(P(OH)(3))(dppe)(2), are formed. The [Ru(P(OMe)(OH)(2))(dppe)(2)]OTf complex also cleaves the Si-H bond in EtMe(2)SiH in a heterolytic fashion, resulting in the trans-Ru(H)(P(OMe)(OH)(2))(dppe)(2) derivative.