Activation of carbon dioxide .6. Ligand effects in the catalytic hydrogenation of carbon dioxide to formic acid using in situ catalysts formed from [{(cod)Rh(mu-Cl)}(2)] and monodentate and bidentate phosphorus ligands

被引:20
作者
Graf, E [1 ]
Leitner, W [1 ]
机构
[1] UNIV REGENSBURG,INST ANORGAN CHEM,D-93040 REGENSBURG,GERMANY
关键词
carbon dioxide; catalytic hydrogenation of; ligand effects; rhodium catalysts; formic acid;
D O I
10.1002/cber.19961290118
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Highly active catalysts for the hydrogenation of CO2 to formic acid in DMSO/NEt(3) are formed in situ from [((cod)Rh(mu-Cl))(2)] and various monodentate or bidentate ligands with phosphorus as the donor atom. Formic acid concentrations up to 2.3 +/- 0.2 mol 1(-1) can be obtained in less than 6 hours at ambient temperature under a total initial pressure of 40 atm by using rhodium concentrations of 5 . 10(-3) mol 1(-1). The changes in catalytic activities observed upon structural changes of monodentate ligands are discussed in terms of classical Ligand parameters like basicity and steric demand of the PR(3) group, while with bidentate ligands R(2)P(CH2)(n)PR(2) the chain length n plays a dominant role for the activity of the catalyst. The effects cannot be explained by a direct impact of the ligand on catalytically active intermediates only, but influences on the formation of these species must also be taken into account.
引用
收藏
页码:91 / 96
页数:6
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