The neutral Rh(I)-Xantphos complex [Rh(κ3-P,O,P-Xantphos)Cl]n, 4, and cationic Rh(III) [Rh(κ3-P,O,P-Xantphos)(H)2][BArF4], 2a, and [Rh(κ3-P,O,P-Xantphos-3,5-C6H3(CF3)2)(H)2][BArF4], 2b, are described [ArF = 3,5-(CF3)2C6H3; Xantphos = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; Xantphos-3,5-C6H3(CF3)2 = 9,9-dimethylxanthene-4,5-bis(bis(3,5-bis(trifluoromethyl)phenyl)phosphine]. A solid-state structure of 2b isolated from C6H5Cl solution shows a κ1-chlorobenzene adduct, [Rh(κ3-P,O,P-Xantphos-3,5-C6H3(CF3)2)(H)2(κ1-ClC6H5)][BArF4], 3. Addition of H2 to 4 affords, crystallographically characterized, [Rh(κ3-P,O,P-Xantphos)(H)2Cl], 5. Addition of diphenyl acetylene to 2a results in the formation of the C-H activated metallacyclopentadiene [Rh(κ3-P,O,P-Xantphos)(ClCH2Cl)(σ,σ-(C6H4)C(H)═CPh)][BArF4], 7, a rare example of a crystallographically characterized Rh-dichloromethane complex, alongside the Rh(I) complex mer-[Rh(κ3-P,O,P-Xantphos)(η2-PhCCPh)][BArF4], 6. Halide abstraction from [Rh(κ3-P,O,P-Xantphos)Cl]n in the presence of diphenylacetylene affords 6 as the only product, which in the solid state shows that the alkyne binds perpendicular to the κ3-POP Xantphos ligand plane. This complex acts as a latent source of the [Rh(κ3-P,O,P-Xantphos)]+ fragment and facilitates ortho-directed C-S activation in a number of 2-arylsulfides to give mer-[Rh(κ3-P,O,P-Xantphos)(σ,κ1-Ar)(SMe)][BArF4] (Ar = C6H4COMe, 8; C6H4(CO)OMe, 9; C6H4NO2, 10; C6H4CNCH2CH2O, 11; C6H4C5H4N, 12). Similar C-S bond cleavage is observed with allyl sulfide, to give fac-[Rh(κ3-P,O,P-Xantphos)(η3-C3H5)(SPh)][BArF4], 13. These products of C-S activation have been crystallographically characterized. For 8 in situ monitoring of the reaction by NMR spectroscopy reveals the initial formation of fac-κ3-8, which then proceeds to isomerize to the mer-isomer. With the para-ketone aryl sulfide, 4-SMeC 6H4COMe, C-H activation ortho to the ketone occurs to give mer-[Rh(κ3-P,O,P-Xantphos)(σ,κ1-4-(COMe)C6H3SMe)(H)][BArF4], 14. The temporal evolution of carbothiolation catalysis using mer-κ3-8, and phenyl acetylene and 2-(methylthio)acetophenone substrates shows initial fast catalysis and then a considerably slower evolution of the product. We suggest that the initially formed fac-isomer of the C-S activation product is considerably more active than the mer-isomer (i.e., mer-8), the latter of which is formed rapidly by isomerization, and this accounts for the observed difference in rates. A likely mechanism is proposed based upon these data.