Taqui Khan, M. M. ; Khan, Badar Taqui ; Jayapal Reddy, P. (1989) Thermodynamics of homogeneous hydrogenation art IX. Hydrogenation of cyclohexene catalyzed by Rh(I) complexes of the monodentate ligands SbPh3, AsPh3 and the bidentate (As, P) ligand 1,2-diphenylphosphino-l ,2-diphenylarsinoethane Journal of Molecular Catalysis, 54 (2). pp. 171-181. ISSN 0304-5102
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Official URL: http://www.sciencedirect.com/science/article/pii/0...
Related URL: http://dx.doi.org/10.1016/0304-5102(89)80213-5
Abstract
The oxidative addition to H2 to the Rh(I) complexes RhCl(SbPh3)31, RhCl(AsPh3)32 and [RhCl(PPh2CH2CH2AsPh2)]23 proceeds at 30°C and 1 atm H2 in 7:3 benzene :ethanol solvent with the formation of the thermodynamically stable cis-dihydrides, as characterized by their hydride proton NMR in situ. The homogeneous hydrogenation of cyclohexene catalysed by complexes 1-3 was investigated in the temperature range 20-50°C at 0.6-1.0 atm of hydrogen partial pressure. Thermodynamic parameters for the formation of the dihydrido Ru(III) complexes and the Rh(I) mono-olefin complexes of 1-3 were computed. The activation parameters corresponding to the rate constant k for the homogeneous hydrogenation of cyclohexene were also calculated. The catalytic activity of the complexes decreases in the order 3 > 2 > 1. Complexes 1 and 2 form more stable hydrides with hydrogen than does complex 3.
| Item Type: | Article |
|---|---|
| Source: | Copyright of this article belongs to Elsevier Science. |
| ID Code: | 58497 |
| Deposited On: | 31 Aug 2011 12:25 |
| Last Modified: | 31 Aug 2011 12:25 |
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