CF bond activation in polyfluorobenzothiolate compounds of Os(III). X-ray structures of [Os(SC6F4(F-2))(SC6F5)2(PMe2Ph)2], [Os(SC6F5)2(o-S2C6F4)(PMe2Ph)] and [Os(C6F5)2(o-S2C6F4)(PMe2Ph)2]

Thermolysis of [Os(SR)3(PMe2Ph)2] (R=C6F5 (1a) or C6HF4-4 (1b)) in refluxing toluene affords [Os(SC6F5)2(o-S2C6F4)(PMe2Ph)] (2a), [Os(SC6HF4)2(o-S2C6HF3)(PMe2Ph)] (2b), and [Os(C6F5)2(o-S2C6F4)(PMe2Ph)2] (3a) through processes involving CF and CS bond cleavage as well as rearrangement of CS bonds. The single-crystal diffraction structures of 1a, 2a and 3a have been determined. In the solid state compound 1a shows a CF→Os interaction.