Kinetics of the hydrogenation of 1-octene catalyzed by [Ni(o-MeO-dppp)(OAc)2]

被引:30
作者
Angulo, IM [1 ]
Bouwman, E [1 ]
机构
[1] Leiden Univ, Leiden Inst Chem, Gorlaeus Labs, NL-2300 RA Leiden, Netherlands
关键词
nickel; phosphane ligands; homogeneous hydrogenation; kinetics; reaction mechanism;
D O I
10.1016/S1381-1169(01)00227-8
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
The kinetics of the nickel-catalyzed hydrogenation of 1-octene have been studied using nickel(II) acetate in combination with the ligand 1,3-bis(di(o-methoxyphenyl)phosphanyl)propane (o-MeO-dppp). The effects of temperature and dihydrogen pressure, as well as the influence of the nickel and substrate concentrations have been studied (T = 30-60 degreesC, p(H-2) = 30-60 bar, [Ni] = 0.35-2.81 mM, [1-octene] = 0.98-3.91 M, ligand/Ni = 1.1 in a mixture of dichloromethane and methanol). The kinetic study results in the surprisingly simple rate law r = k(cat)[Ni][1-octene]p(H-2). The kinetic data are consistent with a mechanism in which the terminating hydrogenolysis step of the nickel-alkyl complex is the rate-determining step of the catalytic cycle with all preceding steps at equilibrium. The first-order dependence on the substrate is confirmed by the results with other substrates, as the hydrogenation rate strongly depends on the nature of the substrate. (C) 2001 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:65 / 72
页数:8
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