Polymeric reagents prepared by exchanging silver(I) for H+ on a macroreticular polystyrene sulfonate ion exchange resin are shown to be capable of selectively absorbing triphenylphosphine from solutions of triphenylphosphine complexes of rhodium(I) and ruthenium(II). Absorption of triphenylphosphine during alkene hydrogenations catalyzed by RhCl(PPh3)3, RuCl2(PPh3)3 and RuHCl(PPh3)3 led to increased hydrogenation rates in hydrogenation of 1‐hexene and other alkenes. Addition of this silver(I) polystyrene sulfonate to alkene hydrogenations catalyzed by HRh(CO) (PPh3)3, RuH2(PPh3)3 and RuH(OCOCH3) (PPh3)3 also led to modest rate accelerations. Catalyst activations seen in these alkene hydrogenations were shown to be due in some cases to triphenylphosphine absorption. In other cases, HCl or HCl plus triphenylphosphine absorption was responsible for the formation of a more active catalyst solution.
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