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This work describes the catalytic hydroesterification and hydroformylation of 1-hexene by [Rh(cod)(amine) 2 ](PF 6 ) complexes (cod = 1,5-cyclooctadiene; amine = pyridine, 2-picoline, 3-picoline, 4-picoline, 3,5-lutidine or 2,6-lutidine) immobilized on poly(4-vinylpyridine) in contact with methanol under carbon monoxide atmosphere. In the presence of these immobilized complexes, 1-hexene, CO and methanol give methyl-heptanoate and 1,1-dimethoxy-heptane as the main reaction products and minor amounts of heptanal. The acetal by-product comes from the nucleophilic addition reaction of the methanol with the formed heptanal. Other products, such as H 2 and CO 2 coming from the catalysis of the water–gas shift reaction are observed. The reaction products distribution depends on the nature of the coordinated amine to the rhodium center and the reaction parameters.

The rhodium(I) complexes, cis-[Rh(CO)2(amine)2](PF6) (amine = pyridine, 2-picoline, 3-picoline, 4-picoline, 3,5-lutidine or 2,6-lutidine) dissolved in methanol under carbon monoxide atmosphere are effective catalysts for the hydroesterification and hydroformylation–acetalization of 1-hexene. In the presence of these soluble complexes, 1-hexene, CO and methanol give methyl-heptanoate and 1,1-dimethoxy-heptane as major products, and minor amounts of heptanal. The acetal product comes from the nucleophilic addition reaction of the methanol with the formed heptanal. Gaseous by-products (H2 and CO2) from the catalysis of the water–gas shift reaction (WGSR) are also observed. The reaction products distribution depends on the nature of the coordinated amine to the rhodium center. The effects of the reaction variables such as CO pressure, temperature, catalyst concentration, 1-hexene/Rh molar ratio and reaction medium, were also examined. These data are discussed in terms of catalytic cycles, and it is concluded that common Rh–H catalytic species are involved.

The catalysis of the hydroesterification and hydroformylation-acetalization of 1-hexene by rhodium(I), cis-[Rh(CO)2(amine)2](PF6) complexes (amine = pyridine, 2-picoline, 3-picoline, 4-picoline, 3,5-lutidine or 2,6-lutidine) dissolved in 10 mL of ethanol or 10 mL of 80% aqueous ethanol, 0.4 mL (3 x 10-3 mol) of 1-hexene, [Rh] = 5 x 10-5 mol, 1-hexene/Rh = 64 under P(CO) = 0.9 atm at 100 °C for 4 h, is described in this work. The mayor products are ethyl-heptanoate, heptanal and 1,1-diethoxyheptane coming from the hydroesterification, hydroformylation reactions and the nucleophilic addition reaction of the ethanol over the formed heptanal, respectively. The reaction product distribution depends on the nature of the coordinate amine to the rhodium center