The complexes cis-[Ru(VI)LO2]2+, cis-[Ru(V)LO2]+ and cis-[Ru(II)L(MeCN)2]2+ (L = N,N,N',N',3,6-hexamethyl-3,6-diazaoctane-1,8-diamine) have been prepared and their structures determined. The two Ru=O bonds in cis-[Ru(VI)LO2]2+ are equivalent [1.795(9) angstrom] and the O Ru-O angle is 112.0(4)-degrees. In cis-[Ru(V)LO2]+ the two Ru=O distances are 1.751(3) and 1.756(4) angstrom, and the O-Ru-O angle is 115.1(2)-degrees. The N(MeCN)-Ru-N(MeCN) angle in cis-[Ru(II)L(MeCN)2]2+ is 86.1(2)-degrees. The cyclic voltammogram of cis-[Ru(VI)LO2]2+ in acetonitrile exhibits a reversible one-electron Ru(VI)-Ru(V) couple at 0.53 V vs. Ag-AgNO3 (0.1 mol dm-3). In aqueous solutions, proton-coupled electron-transfer redox couples are observed. This complex is capable of oxidising a wide variety of organic substrates including 2,3-dimethylbutane and adamantane. Oxidation of saturated alkanes occurred preferentially at the tertiary C-H bond.