期刊
JOURNAL OF ORGANOMETALLIC CHEMISTRY
卷 689, 期 23, 页码 3782-3792出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/j.jorganchem.2004.06.051
关键词
hydroformylation; rhodium; phosphines; aqueous biphasic catalysis
The complexes RhH(CO)L-3, where L = PPh3, P(m-C6H4SO3Na)(3) (TPPTS), and (C6H5)(2)P(m-C6H4SO3Na) (TPPMS) were used as catalyst precursors for a comparative study of the catalytic hydroformylation of several C6 alkenes and alkene mixtures under moderate reaction conditions in homogeneous (PPh3) and aqueous-biphasic (TPPTS, TPPMS) media. The biphasic systems are efficient for the hydroformylation of hex-1-ene, 2,3-dimethyl-1-butene, styrene, cyclohexene, and mixtures thereof, in water/n-heptane at 80 degreesC. The main problem associated with these catalysts is their tendency to promote alkene isomerization if the effective syngas concentration in the liquid phases is low, but this side-reaction can be suppressed by using higher CO/H-2 pressures (54 atm). The selectivity of both water-soluble catalysts for linear products of hex-1-ene and for branched products of styrene is modest in comparison with the homogeneous system, which may limit their utility for classical oxo uses, but this is not a disadvantage for other interesting applications related to the hydroformylation of alkene mixtures and particularly to naphtha upgrading where linear and branched products are equally useful. The catalysts can be recycled without significant loss of activity and are resistant to the presence of benzothiophene in the mixture. (C) 2004 Elsevier B.V. All rights reserved.
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