可溶于水的钉原子簇新体系催化丙烯和乙烯的醛化

HYDROFORMYLATION OF PROPYLENE AND ETHYLENE WITH CO/H_2 CATALYZED BY WATER-SOLUBLE TRIRUTHENIUM CLUSTER Ru_3 ( CO ) _9 ( Ph_2P-m-C_6H_4SO_3Na )_3

1.前言 近年来,随着金属簇合物合成化学的迅速发展,已出现了一类可溶于水的金属簇合物。分子中含有55个金属原子的可溶于水的簇合物Au_(55)[Ph_2PC_6H_4SO_3Na)_12Cl_6已被合成和表征。金属簇合物被期待发挥特异的催化性能。用水作反应溶剂,好处很多。水不仅便宜易得,反应原料气无须经除水净化,反应体系简单,而且某些反应。

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 ratio 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.