1-Pentene Hydroformylation Catalyzed by Polymer-Bound Ruthenium Complexes

Article abstract of DOI:10.1021/jo00322a031

Polymer-bound ruthenium hydroformylation catalysts were prepared by reacting diphenylphosphinated styrene-1percent divinylbenzene resins with Ru(CO)3(PPh3)2 under a carbon monoxide atmosphere.Resins with 29percent and 5percent ring-substitution loading levels of phosphine were prepared, and resins with P/Ru ratios of 3.1, 6.7, and 11.3 were made with the 29percent phosphine loading.These resins functioned as 1-pentene hydroformylation catalysts and were compared to the homogeneous use of Ru(CO)3(PPh3)2 as the catalyst.No olefin isomerization occured.The resin catalysts with P/Ru ratios of 3.1 and 6.7 at 29percent loading gave higher n/b aldehyde selectivities (3.5-3.8) than the homogeneous catalyst when employed at P/Ru ratios of 20 but not as high as was achieved by using Ru(CO)3(PPh3)2 in molten PPh3 (5.1).The n/b selectivity was discussed in terms of the equilibrium between (polymer-PPh2)2RuH2(alkene)(CO) and polymer-PPh2RuH2(alkene)(CO)2 within the resin matrix where phosphine loading, P/Ru, ligand mobility, and swelling play contributing roles.The novel 1,1'-bis(diphenylphosphino)ferrocene ligand induced higher n/b selectivities than PPh3 in homogeneous Ru-catalyzed reactions.