The ruthenium aqua complexes [cp*Ru(OH₂)(N–N)](OTf) (cp* = η⁵-pentamethylcyclopentadienyl, N–N = 2,2′-bipyridine, phen = 1,10-phenanthroline, OTf⁻ = trifluoromethanesulfonate) and the acetonitrile complex [cpRu(CH₃CN)(bipy)](OTf) (cp = η⁵-cyclopentadienyl) are water-, acid-, and thermally stable (>200 °C) catalysts for the hydrogenation of aldehydes and ketones in sulfolane solution. In the presence of HOTf as a co-catalyst, they effect the deoxygenation of 1,2-hexanediol to 1-hexanol and hexane. Glycerol is deoxygenated to 1-propanol in up to 18% yield and under more forcing conditions completely deoxygenated to propene. The structure of the acetonitrile pro-catalyst [cpRu(CH₃CN)(bipy)](OTf) has been determined by X-ray crystallography (space groupP (a = 9.3778(10) Å; b = 10.7852(10) Å; c = 11.1818(13) Å; α = 101.718(5)°; β = 114.717(4)°; γ = 102.712(5)°; R = 3.95%).