The ‘Ru(η-C₅Me₅)⁺’ fragment generated by protonation of [{Ru(η-C₅Me₅)(OMe)}₂] by CF₃SO₃H, reacted with cyclohexene sulfide to give [Ru(η-C₅Me₅)(η⁶-C₆H₆)]⁺1 and H₂S. With 1,4-dithiane no C–S bond activation was observed but instead the successive formation of [Ru(η-C₅Me₅)(S₂C₄H₈)(CF₃SO₃)]2 and [Ru(S₂C₄H₈)₃]²⁺3, whereas with 1,3-dithiane two compounds resulting from the sequential activation of C–S bonds were isolated as CF₃SO₃^– salts, namely [{Ru(η-C₅Me₅)(SMe)(SCH₂CHCH₂)}₂]²⁺4 and [{Ru[C₅Me₄CH₂S(CH₂)₃SMe]}₂]²⁺5. The fragment also reacted with neat dichloromethane to give two trinuclear clusters: [{Ru(η-C₅Me₅)}₃(µ-Cl)₃(µ₃-CH)]⁺6 and [{Ru(C₅Me₅)}₃(µ-Cl)₂(µ-CO)(µ₃-CH)]²⁺7 in 60 and 30% yield respectively. Its reaction with chlorocyclohexane, 1,2-dichlorocyclohexane and 1,2,3,4,5,6-hexachlorocyclohexane (lindane) yielded 1 and various amounts of H₂ and HCl. In the case of lindane the conversion was only 30% and yielded a 9:1 mixture of 1 and [Ru(η-C₅Me₅)(η⁶-C₆H₅Cl)]⁺9. Finally the reaction of C–Cl versus C–O bond activation was compared using 2-chlorocyclohexanone, 2-chlorocyclohexanol and 2,2,6,6-tetrachlorocyclohexanol. It was found that in all cases the C–Cl activation was easier. The first reaction yielded 1, the second the new trinuclear cluster [{Ru(C₅Me₅)}₃(µ-Cl)₂(µ-CO)(µ₃-CCl)]²⁺11 similar to 7. The latter reaction depended upon the reaction conditions, but in tetrahydrofuran at 80 °C, an 80% conversion was observed yielding a 1:7: < 1 mixture of 1, [Ru(η-C₅Me₅)(η⁶-C₆H₅OH)]⁺10 and [Ru(η-C₅Me₅)(η⁶-C₆H₅Cl)]⁺9 thus demonstrating a high selectivity for C–Cl activation in the presence of C–O bonds.