Hydrogenation and isomerization of 1-hexene with Ru3(CO)9(PPh2CH2CH2Si(OMe)3)3 immobilized in silica matrices via the sol-gel method

被引:11
作者
Dallmann, K [1 ]
Buffon, R [1 ]
机构
[1] Univ Estadual Campinas, UNICAMP, Inst Quim, BR-13083970 Campinas, SP, Brazil
基金
巴西圣保罗研究基金会;
关键词
sol-gel process; ruthenium clusters; hydrogenation;
D O I
10.1016/S1381-1169(02)00022-5
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
Ru-3(CO)(9)(PPh3)(3) and Ru-3(CO)(9(P)Ph2CH2CH2Si(OMe)(3))(3) have been heterogenized in silica matrices by the sol-gel method. Gels prepared with Ru-3(CO)(9)(PPh2CH2CH2Si(OMe)(3))(3) were tested in the hydrogenation and isomerization of 1-hexene. At H-2-pressures of 16 psi in repeated runs (15h, 90degreesC) turnover numbers for 1-hexene hydrogenation were between 380 and 460. Isomerization products were trans-2-hexene, cis-2-hexene and trans-3-hexene. No cis-3-hexene, 2-methyl-1-pentene and 2-methylpentane were found. Leaching of ruthenium in each run was around 0.05% of ruthenium present in the original gel. UV-VIS and FT-IR spectra of the pure cluster compounds and the gels before and after the catalytic reactions showed that during the gel preparation some Ru-3 units remain intact, but are cleaved when the gel is heated under vacuum or used in catalytic hydrogenation reactions. (C) 2002 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:187 / 194
页数:8
相关论文
共 25 条
[1]   CHARACTERIZATION OF SUPPORTED RHODIUM AND RUTHENIUM CARBONYL CLUSTERS BY EXAFS SPECTROSCOPY [J].
BINSTED, N ;
EVANS, J ;
GREAVES, GN ;
PRICE, RJ .
ORGANOMETALLICS, 1989, 8 (03) :613-620
[2]  
BRINKER CJ, 1990, SOL GEL SCI PHYS CHE, P522
[3]  
CANDLIN JP, 1966, CHEM IND, V19, P1960
[4]   Hydrogenation and isomerization of 1-hexene with Ru3(CO)12 and Ru3(CO)9(PPh3)3 [J].
Dallmann, K ;
Buffon, R .
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 2001, 172 (1-2) :81-87
[5]  
DALLMANN K, 2000, CATAL COMMUN, V1, P9
[6]  
DOI Y, 1984, INORG CHIM A-ART LET, V90, pL7, DOI 10.1016/S0020-1693(00)80711-2
[7]   ANCHORING OF COBALT, RUTHENIUM, AND OSMIUM CARBONYLS TO OXIDES BY PENDANT THIOL AND PHOSPHINE-LIGANDS [J].
EVANS, J ;
GRACEY, BP .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1982, (06) :1123-1129
[8]   SPECTROSCOPIC STUDIES ON ABSORBED METAL-CARBONYLS .2. INTERACTION OF [RU3(CO)12] WITH SILICA, TITANIA, AND ALUMINA [J].
EVANS, J ;
MCNULTY, GS .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1984, (06) :1123-1131
[9]   PREPARATION AND CATALYTIC PROPERTIES OF ANCHORED RUTHENIUM AND RHODIUM CLUSTERS [J].
KIISKI, U ;
PAKKANEN, TA ;
KRAUSE, O .
JOURNAL OF MOLECULAR CATALYSIS, 1989, 50 (02) :143-151
[10]   Selective hydrogenation of toluene over ruthenium catalysts prepared by the sol-gel method [J].
Kluson, P ;
Had, J ;
Belohlav, Z ;
Cerveny, L .
APPLIED CATALYSIS A-GENERAL, 1997, 149 (02) :331-339