Reactions of the aryl complexes Rh(aryl){κ3-P,O,P-[xant(PiPr2)2]} (1; aryl = 3,5-Me2C6H3 (a), C6H5 (b), 3,5-Cl2C6H3 (c), 3-FC6H4 (d); xant(PiPr2)2 = 9,9-dimethyl-4,5-bis-(diisopropylphosphino)xanthene) with O2, CO, and MeO2CC≡CCO2Me have been performed. Under 1 atm of O2, the pentane solutions of complexes 1 afford the dinuclear peroxide derivatives [Rh(aryl){κ2-P,P-xant(PiPr2)2}]2(μ-O2)2 (2a–2d) as yellow solids. In solution, these species are unstable. In dichloromethane, at room temperature, they are transformed into the dioxygen adducts Rh(aryl)(η2-O2){κ3-P,O,P-[xant(PiPr2)2]} (3a–3d), as a result of the rupture of the double peroxide bridge and the reduction of the metal center. Complex 3b decomposes in benzene, at 50 °C, to give diphosphine oxide, phenol, and biphenyl. Complexes 1 react with CO to give the square-planar mono carbonyl derivatives Rh(aryl)(CO){κ2-P,P-[xant(PiPr2)2]} (4a–4d), which under carbon monoxide atmosphere evolve to benzoyl species Rh{C(O)aryl}(CO){κ2-P,P-[xant(PiPr2)2]} (5a–5d), resulting from the migratory insertion of CO into the Rh-aryl bond and the coordination of a second CO molecule. The transformation is reversible; under vacuum, complexes 5 regenerate the precursors 4. The addition of the activated alkyne to complexes 1b and 1d initially leads to the π-alkyne intermediates Rh(aryl){η2-C(CO2Me)≡C(CO2Me)}{κ3-P,O,P-[xant(PiPr2)2]} (6b, 6d), which evolve to the alkenyl derivatives Rh{(E)-C(CO2Me)=C(CO2Me)aryl}{κ3-P,O,P-[xant(PiPr2)2]} (7b, 7d). The diphosphine adapts its coordination mode to the stability requirements of the different complexes, coordinating cis-κ2-P,P in complexes 2, fac-κ3-P,O,P in compounds 3, trans-κ2-P,P in the mono carbonyl derivatives 4 and 5, and mer-κ3-P,O,P in products 6 and 7.