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 $Ru(P(OH)_{3})(dppe)_{2}^{2+}$

摘要

The highly electrophilic, 16-electron, coordinatively unsaturated $[Ru(P(OMe)(OH)_{2})(dppe)_{2}][OTf]_{2}$ 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, $[Ru(P(OH)Adppe)_{2}]^{2+}$, are formed. The $[Ru(P(OMe)(OH)_{2})(dppe)_{2}][OTf]_{2}$ 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.