Trinuclear rhodium complexes and their relevance for asymmetric hydrogenation

Chemistry - An Asian Journal

Volumn 3, Issue 11, 2008, Pages 1979-1982

  Preetz, Angelika ^a   Baumann, Wolfgang ^a   Drexler, Hans Joachim ^a   Fischer, Christian ^a   Sun, Jiangtao ^a   Spannenberg, Anke ^a   Zimmer, Oswald ^b   Hell, Wolfgang ^b   Heller, Detlef ^a  

^a LEIBNIZ INSTITUT FÜR KATALYSE E V AN DER UNIVERSITÄT ROSTOCK   (Germany)

^b GRÜNENTHAL GMBH   (Germany)

Author keywords

Asymmetric catalysis; Hydrogenation; Kinetics; Phosphine ligands; Rhodium

Indexed keywords

EID: 55449134972     PISSN: 18614728     EISSN: 1861471X     Source Type: Journal    
DOI: 10.1002/asia.200800184     Document Type: Article

References (32)

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7. b) "Catalyst Inhibition and Deactivation in Homogeneous Hydrogenation":D. Heller, A. H. M. de Vries, J. G. de Vries in Handbook of Homogeneous Hydrogenation (Eds.: H. G. deVries and C. Elsevier), Wiley-VCH, Weinheim, 2007, chap. 44, pp. 483-1516.
8. Regarding the possible influence of arene complexes on the activity of asymmetric hydrogenations, see: D. Heller, H.-J. Drexler, A. Spannenberg, B. Heller, J. You, W. Baumann, Angew. Chem. 2002, 114, 814-817;
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17. Further examples as well as a tabular summary of important bond lengths and angles can be found in the Supporting Information. CCDC 680135-680141 contain the supplementary crystallographic data to this publication. These data can be obtained free of charge via the Internet at www.ccdc.cam.ac.uk/conts/ retrieving.html or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB21EZ; Fax:(+44) 1223-336-033; E-mail: deposit@ccdc.cam.ac.uk.
18. 2O mixture; or by subsequent exchange of one anion (see the Supporting Information).
19. a) M. Ebihara, M. Iiba, S. Higashi, N. Tsuzuki, T. Kawamura, T. Morioka, S. Ozawa, T. Yamabe, H. Masuda, Polyhedron 2003, 22, 3413-3422;
20. b) A. V. de Miguel, K. Isobe, P. M. Bailey, N. J. Meanwell, P. M. Maitlis, Organometallics 1982, 1, 1604-1607;
21. c) H. Seino, Y. Mizobe, M. Hidai, Organometallics 2000, 19, 3631-3639.
22. In metal atom clusters direct metal-metal bonds exist, whereas in "Werner complexes" nuclei are bridged by μ-bridging ligands.
23. The Supporting Information provides all NMR data of the synthesized trinuclear complexes as well as NMR data of several dipamp complexes.
24. An analogous spectrum for the dipamp ligand can be found in the Supporting Information.
25. 31P NMR spectrum exhibits signals of the trinuclear complex only. The solvate complex which is expected from the equilibrium is not observed in a period of weeks.
26. 4 that had been exposed to air for 10 days shows only two species: the doublet of the trinuclear complex and a singlet (most likely of an oxide) at δ = 31 ppm (ratio of integrals trinuclear complex/oxide = 70:30).
27. The general procedure for hydrogenations is described in: "Kinetics in Homogeneous Hydrogenation: Interpretation and Measurement": H.-J. Drexler, A. Preetz, T. Schmidt, D. Heller in Handbook of Homogeneous Hydrogenation (Eds.: H. G. deVries, C. Elsevier), Wiley-VCH, Weinheim, 2007, chap. 10, pp. 257-293.
28. While the hydrogenations with the solvate complex and with the cod complex result in an ee value of 96%, the hydrogenation with the trinuclear complex gives reproducibly 89% ee. The reasons remain unclear.
29. Rh = -967.2 ppm.
30. +".
31. H. U. Blaser, F. Spindler, M. Studer, Appl. Catal. A 2001, 221, 119-143 (Table 5).
32. It should also be kept in mind that the addition of acid to a basic substrate can as well lead to a protonation of the latter. Thus, it could not act as a base anymore to initiate the formation of trinuclear complexes. In this context the importance of the order in which components are added to the reaction solution to be hydrogenated becomes clear.