Formylation with supercritical carbon dioxide over Ru/Al2O3 modified by phosphines:: heterogeneous or homogeneous catalysis?

被引：18

作者：

Rohr, M ^{[1
]}

Grunwaldt, JD ^{[1
]}

Baiker, A ^{[1
]}

机构：

[1] Swiss Fed Inst Technol, ETH Honggerberg, Dept Chem & Appl Biosci, CH-8093 Zurich, Switzerland

来源：

JOURNAL OF CATALYSIS | 2005年 / 229卷 / 01期

关键词：

formylation of amines; 3-methoxypropylamine; supercritical carbon dioxide; Ru/Al2O3; phosphines; X-ray absorption spectroscopy; EXAFS; in situ spectroscopy;

D O I：

10.1016/j.jcat.2004.09.026

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：

The formylation of 3-methoxypropylamine with hydrogen and "supercritical" carbon dioxide over Ru-based catalysts was studied. In this solventless process, carbon dioxide acts as both reactant and solvent. Interestingly, Ru/Al2O3 modified by the phosphine 1,2-bis(diphenylphosphino)ethane (dppe) showed a high formylation activity at 100% selectivity, comparable to those of the homogeneous catalysts RuCl2(dppe)(2) and RuCl2(PPh3)(3). Analysis of the reaction mixture by ICP-OES and structural studies by in situ X-ray absorption spectroscopy discovered that the presence of the phosphine modifier led to the formation of a homogeneous ruthenium catalyst. (C) 2004 Elsevier Inc. All rights reserved.

引用

页码：144 / 153

页数：10

共 51 条

[1]

[Anonymous], 1999, CHEM SYNTHESIS USING

[2]

Aresta M, 1997, CHEMTECH, V27, P32

[3]

Baiker A, 2000, APPL ORGANOMET CHEM, V14, P751, DOI 10.1002/1099-0739(200012)14:12<751::AID-AOC85>3.0.CO

[4]

2-J

[5] Mechanisms of reactions of dihydrogen complexes:: Formation of trans-[RuH(H2)(dppe)2]+ and substitution of coordinated dihydrogen [J].

Basallote, MG ;

Durán, J ;

Fernández-Trujillo, MJ ;

Máñez, MA .

INORGANIC CHEMISTRY, 1999, 38 (22) :5067-5071

[6] Limits and advantages of x-ray absorption near edge structure for nanometer scale metallic clusters [J].

Bazin, D ;

Rehr, JJ .

JOURNAL OF PHYSICAL CHEMISTRY B, 2003, 107 (45) :12398-12402

[7]

BAZIN D, 1996, XRAY ABSORPTION FINE, V2

[8] CARBON-DIOXIDE AS AN ALTERNATIVE C1 SYNTHETIC UNIT - ACTIVATION BY TRANSITION-METAL COMPLEXES [J].

BEHR, A .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1988, 27 (05) :661-678

[9] NEW PREPARATIONS AND MOLECULAR-STRUCTURES OF CIS-MCL2(PH2PCH2PPH2)2, CIS-RUCL2(PH2PCH2PPH2)2, CIS-OSCL2(PH2PCH2PPH2)2 AND TRANS-RUCL2(PH2PCH2PPH2)2 [J].

CHAKRAVARTY, AR ;

COTTON, FA ;

SCHWOTZER, W .

INORGANICA CHIMICA ACTA-ARTICLES AND LETTERS, 1984, 84 (02) :179-185

[10] INFLUENCE OF CHLORIDE VERSUS HYDRIDE ON H-H BONDING AND ACIDITY OF THE TRANS DIHYDROGEN LIGAND IN THE COMPLEXES TRANS-[RU(H2)X(PR(2)CH(2)CH(2)PR(2))(2)](+), X=CL, H, R=PH, ET - CRYSTAL-STRUCTURE DETERMINATIONS OF [RUCL(DPPE)(2)]PF6 AND TRANS-[RU(H2)CL(DPPE)(2)]PF6 [J].

CHIN, B ;

LOUGH, AJ ;

MORRIS, RH ;

SCHWEITZER, CT ;

DAGOSTINO, C .

INORGANIC CHEMISTRY, 1994, 33 (26) :6278-6288

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