可溶于水的钉原子簇新体系催化丙烯和乙烯的醛化

Abstract

[英文摘要]Water-soluble and air-stable triruthenium carbonyl cluster Ru3 (CO)9(dpm)3(dpm=sodium diphenylphosphinobenzene-m-sulphonate)was used as catalyst to hydroformylate propylene and ethylene with syngas in water. For propylene hydroformylation, the main product is n-butyraldehyde, side-products are iso-butyraldehyde and a small amount of 1-butyl and isobutyl alcohols.At 120℃ and propylene,CO and H2 partial pressures of 0.7 MPa, 2.0 MPa and 2.0 MPa respectively, catalytic turnover of 61.2 mol·products/mol·cluster·h and product n/i natio of 15.9 were obtained.Under milder reaction conditions (temperature;80~120℃,total gas pressure:2.7~5.0 MPa),catalytic activity was found to rise with the increase of reaction temperature,catalyst concentration or partial pressures of the gaseous reagents (CO/H2=1).The effect of temperature increase was found to be the most remarkable.The effect of pH value to the reaction was investigated and neutral water was found to be most suitable.In the case of ethylene,the main product is propionaldehyde;side-products (15-35%)are diethyl ketone,3-pentanol and a small amount of 1-propanol.The catalyst was characterized before and after the reactions by IR and X-ray photoelectron spectroscopy and the results were discussed as related to the possible catalytic active species.