HOMOGENEOUS CATALYTIC-HYDROGENATION OF SUPERCRITICAL CARBON-DIOXIDE
HOMOGENEOUS CATALYTIC-HYDROGENATION OF SUPERCRITICAL CARBON-DIOXIDE
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DOI：
10.1038/368231a0
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发表时间：
1994-03-17
期刊：
影响因子：
64.8
通讯作者：
NOYORI, R
中科院分区：
文献类型：
--
作者：
JESSOP, PG;IKARIYA, T;NOYORI, R
使用二氧化碳作为合成有机化合物的起始原料一直是合成化学家的目标。将二氧化碳氢化成甲酸、甲醇和其它有机物质是特别有吸引力的，但仍然是困难的。最近已经描述了这种甲酸路线，其基于在二甲基亚砜（1）和水性溶剂（2）中使用有机金属铑催化剂。我们在这里报告的有效生产甲酸在二氧化碳和氢的超临界混合物中含有催化钌（II）膦络合物。氢在其中高度混溶的超临界相的使用导致非常高的初始反应速率-高达1，400摩尔甲酸每摩尔催化剂每小时。在相同条件下但在液体有机溶剂中的相同反应要慢得多。我们的研究结果表明，超临界流体代表了一个有前途的介质均相催化。
THE use of carbon dioxide as a starting material for the synthesis of organic compounds has long been a goal for synthetic chemists. The hydogenation of carbon dioxide to formic acid, methanol and other organic substances is particularly attractive, but has remained difficult. This route to formic acid has been described recently, based on the use of organometallic rhodium catalysts in dimethyl sulphoxide(1) and aqueous(2) solvents. We report here the efficient production of formic acid in a supercritical mixture of carbon dioxide and hydrogen containing a catalytic ruthenium(II) phosphine complex. The use of a supercritical phase, in which hydrogen is highly miscible, leads to a very high initial rate of reaction-up to 1,400 moles of formic acid per mote of catalyst per hour. The same reaction under identical conditions but in liquid organic solvents is much slower. Our results suggest that supercritical fluids represent a promising medium for homogeneous catalysis.