The complexes [Cp*RuCl((Pr2PSX)-Pr-i)] (X = pyridyl, quinolyl) react directly with alcohols ROH (R = Me, Et, Pr-i, Pr-n) and NaBPh4, affording the novel cationic hydrido(alkoxo) derivatives [Cp*RuH(OR)((Pr2PSX)-Pr-i)]-[BPh4]. These ruthenium(IV) compounds result from the formal oxidative addition of the alcohol to the 16-electron fragment {[Cp*Ru((Pr2PSX)-Pr-i)](+)}, generated in situ upon chloride dissociation. The hydrido(alkoxo) complexes are reversibly deprotonated by a strong base such as KOBut, yielding the neutral alkoxides [Cp*Ru(OR)-((Pr2PSX)-Pr-i)], which are remarkably stable toward beta elimination and do not generate the corresponding hydrides. The hydrido(alkoxo) complexes undergo a slow electron-transfer process, releasing H-2 and generating the dinuclear ruthenium(III) complex [{Cp*Ru(kappa(2)-N,S-mu S-SC5H4N)}(2)][BPH4](2). In this species, the Ru-Ru separation is very short and consistent with what is expected for a Ru Ru triple bond.