A molecular model to explain and predict the stereoselectivity in rhodium-catalyzed hydroformylation

Organometallics

Volumn 17, Issue 11, 1998, Pages 2141-2143

  Gleich, Dieter ^a   Schmid, Rochus ^b   Herrmann, Wolfgang A ^a  

^a TECHNICAL UNIVERSITY OF MUNICH   (Germany)

^b UNIVERSITY OF CALGARY   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001346731     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om9801397     Document Type: Article

References (38)

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2. Reviews: (a) Herrmann, W. A.; Cornils, B. Angew. Chem., Int. Ed. Engl. 1997, 36, 1047. (b) Cornils, B.; Herrmann, W. A. In Applied Homogeneous Catalysis with Organometallic Compounds; VCH-Wiley: Weinheim, 1996; Vol. 1, pp 3-25. (c) Cornils, B.; Herrmann, W. A.; Rasch, M. Angew. Chem., Int. Ed. Engl. 1994, 33, 2144.
3. Reviews: (a) Herrmann, W. A.; Cornils, B. Angew. Chem., Int. Ed. Engl. 1997, 36, 1047. (b) Cornils, B.; Herrmann, W. A. In Applied Homogeneous Catalysis with Organometallic Compounds; VCH-Wiley: Weinheim, 1996; Vol. 1, pp 3-25. (c) Cornils, B.; Herrmann, W. A.; Rasch, M. Angew. Chem., Int. Ed. Engl. 1994, 33, 2144.
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27. The calculations on the BP86/DZVP//LDA/DZVP level (cf. refs 16 and 17a) are related to Morokuma's ab initio (HF and MP2) results (cf. ref 7) but aim at complexes with two phosphorus ligands. All DFT calculations were performed with the program DGauss (DGauss, Release 3.0, Cray Research Inc., 1995; cf. ref 17b).
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33. Force field parameters were derived as far as possible to reproduce the DFT structure of the reaction center. The approximately trigonal-bipyramidal metal coordination was regulated by soft restraints implemented in the force field. Atomic charges other than those of aryl rings were neglected. A detailed description of the parametrization process can be found in refs 13a and 14. Parameters for phosphorus are listed in ref 11a; further parameters are given as Supporting Information.
34. Suitable initial structures were subject to two independent MD simulations: (1) The temperature (1000 K) was held constant for 100 ps. Every picosecond the structure was minimized. (2) There were 2.4 ps cycles with falling temperature (1000-300 K) and two minimizations repeated 50 times. The first minimization was done after a 0.5 ps sampling at 1000 K, the second after a 0.5 ps sampling at 300 K. Between these two samplings, the temperature was lowered by 50 K steps every 0.1 ps. The lowest energy structures of both simulations (which have proven to be identical) were taken as global minima. The calculations of ee's follow the formula (2 iso transition states a and b, T = 298 K) (Equation Presented) In this formula, changes of temperature have only a small influence. All MM calculations were performed with the Insight/Discover program package (Insight/Discover, Release 95.0, BIOSYM/MSI: San Diego, 1995).
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36. (a) MM calculations suggest a rather rigid ligand structure with a natural bite angle near 90° (cf. refs 5c, 13a, 14, and 22b).
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