The ruthenium triflate complex Cp*(PiPr3)RuOTf (1) was generated from the reaction of Cp*(PiPr3)RuCl with Me3SiOTf in dibutyl ether. Complex 1 reacted with primary and secondary silanes to produce a family of Ru(IV) silyl dihydride complexes of the type Cp*(PiPr3)Ru(H)2(SiRR′OTf) (3–12). Structural analyses of complexes 8 (R = R′ = Ph) and 12 (R = R′ = fluorenyl) revealed the presence of a tetrahedral silicon center and a four-legged piano stool geometry about ruthenium. Anion abstraction from Cp*(PiPr3)Ru(H)2(SiHROTf) by [Et3Si·toluene][B(C6F5)4] afforded hydrogen-substituted cationic ruthenium silylene complexes [Cp*(PiPr3)Ru(H)2(═SiHR)][B(C6F5)4] (R = Mes (13), R = Si(SiMe3) (14)) that display a significant Ru–H···Si interaction, as indicated by relatively large 2JSiH coupling constants (2JSiH = 58.2 Hz (13), 2JSiH = 37.1 Hz (14)). The syntheses of secondary silylene complexes [Cp*(PiPr3)Ru(H)2(═SiRR′)][B(C6F5)4] (R = R′ = Ph (15); R = Ph, R′ = Me (16), R = R′ = fluorenyl (17)) were also achieved by anion abstraction with [Et3Si·toluene][B(C6F5)4]. Complexes 15–17 do not display strong Ru–H···Si secondary interactions, as indicated by very small 2JSiH coupling constant values.
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