CATALYTIC ACTIVITY OF RUTHENIUM 2,2'-BIPYRIDINE DERIVED CATALYSTS IN 1-HEXENE HYDROFORMYLATION AND 1-HEPTANAL HYDROGENATION

被引:35
作者
HAUKKA, M [1 ]
ALVILA, L [1 ]
PAKKANEN, TA [1 ]
机构
[1] UNIV JOENSUU,DEPT CHEM,SF-80101 JOENSUU,FINLAND
关键词
BIPYRIDINE; CARBONYL COMPLEXES; HEPTANOL; HEXENE; HYDROFORMYLATION; HYDROGENATION; RUTHENIUM; SUPPORTED CATALYSTS;
D O I
10.1016/1381-1169(95)90043-8
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Method and conditions of preparation strongly affect the hydroformylation activity of the ruthenium cluster derived Ru-3(CO)(12)/2,2'-bipyridine/SiO2 catalyst. The highest activities have been achieved with a dichloromethane impregnated catalyst. A major problem with this catalyst is poor reproducibility of the hydroformylation activity, probably due to uncontrolled formation of several supported surface species, Reproducibility can be improved by using a non-chlorinated impregnation solvent such as tetrahydrofurane. In hydroformylation, Ru-3(CO)(12)/2,2'-bipyridine/SiO2 has a strong tendency to convert alkenes directly to alcohols. The limiting step in this process is the initial hydrocarbonylation of alkenes to aldehydes. Ru-3(CO)(12)/2,2'-bipyridine/SiO2 catalyzes the second step, hydrogenation of aldehydes to alcohols, in good yield. Use of an effective, aldehyde-producing cocatalyst such as Rh together with Ru-3(CO)(12)/2,2'-bipyridine/SiO2 allows very high alcohol yields to be achieved. The detailed surface structure of Ru-3(CO)(12)/2,2'-bipyridine/SiO2 is not known, but one probable active species is oligomeric or polymeric [{Ru(bpy) (CO)(2)}(n)]. Monomeric and dimeric ruthenium monobipyridines showed at most only moderate activity in hydroformylation. By contrast, [Ru(bpy)(CO)(2)Cl(C(O)OCH3)] and [Ru(bpy)(CO)(2)ClH] are highly active in hydrogenation of C-7 aldehydes to C-7 alcohols.
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页码:79 / 92
页数:14
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