We thank the EPSRC (UK) for a rolling grant to J.M.T. and general support to B.F.G.J., KDMH and a studentship to MDJ, and for financial assistance towards the single crystal diffractometers. We also thank Bayer AG, Leverkusen (Germany) for their support to R.R., the Marie Curie fellowship Scheme for J.R., ICI and the Newton trust for M.D.J‥ We gratefully acknowledge Dr. J. E. Davies for determining the crystal structures. Dr. S. Kitchin is acknowledged for the 19F MAS measurements and Mr. G. Burns for technical assistance.
Enhancing the Enantioselectivity of Novel Homogeneous Organometallic Hydrogenation Catalysts†
Article first published online: 17 SEP 2003
Copyright © 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Angewandte Chemie International Edition
Volume 42, Issue 36, pages 4326–4331, September 22, 2003
How to Cite
Jones, M. D., Raja, R., Thomas, J. M., Johnson, B. F. G., Lewis, D. W., Rouzaud, J. and Harris, K. D. M. (2003), Enhancing the Enantioselectivity of Novel Homogeneous Organometallic Hydrogenation Catalysts. Angew. Chem. Int. Ed., 42: 4326–4331. doi: 10.1002/anie.200250861
- Issue published online: 17 SEP 2003
- Article first published online: 17 SEP 2003
- Manuscript Revised: 26 MAY 2003
- Manuscript Received: 27 DEC 2002
- 1Homogeneous Catalysis, 2nd ed., Wiley, New York, 1992., ,
- 2Applied Homogeneous Catalysis with Organometallic Compound, Vol. 1 (Eds.: B. Cornils, W. A. Herrmann), Wiley-VCH, Weinheim, 1996, pp. 206, and references therein.in
- 3aAsymmetric Catalysis in Organic Synthesis, Wiley, New York, 1994;,
- 3cCatalytic Asymmetric Synthesis, VCH, Weinheim, 1993.,
- 4Chem. Commun. 2000, 961., , , , , , , ,
- 6Though relatively uncommon, diamino ligands in organometallic complexes that are catalytic for hydrogenation were reported. For example,
- 6fOrganometallics 1996, 15, 9163;, , ,
- 7Crystallographic data: 1 a Rh COD complex C15H28BF4N2Rh, M=426.11 g mol−1, yellow prisms 0.28×0.14×0.07 mm, monoclinic, a=9.1422(2) Å, b=10.8050(4) Å, c=9.3369(3) Å, β=110.243(2)°, V=865.34(5) Å3, T=180(2) K, space group P21, Z=2, 5542 reflections collected, 3400 independent reflections (Rint=0.0286), refinement method: full matrix least squares on F2, final R1=0.0254, wR2=0.0588, GOF=1.125. 1 a Rh NBD complex C14H24BF4N2Rh, M=410.07 g mol−1, yellow prisms 0.25×0.12×0.12 mm, orthorhombic, a=9.3033(2) Å, b=10.4587(3) Å, c=16.7856(5) Å, β=90°, V=1633.25 Å3, T=180(2) K, space group P212121, Z=4, 9724 reflections collected, 3359 independent reflections (Rint=0.1154), refinement method: full matrix least squares on F2, final R1=0.0591, wR2=0.1278, GOF=0.991. 1 a Pd complex C10H21BF4N2Pd, M=362.50 g mol−1, clear prisms 0.30×0.18×0.12 mm, orthorhombic, a=8.0393(3) Å, b=12.8833(4) Å, c=13.8562(5) Å, β=90°, V=1435.12(9) Å3, T=180(2) K, space group P21, Z=2, 8364 reflections collected, 3190 independent reflections (Rint=0.0319), refinement method: full matrix least squares on F2, final R1=0.0303, wR2=0.0700, GOF=1.032, crystallographic data is available in the .cif format. CCDC-193929 (1 a Rh COD), CCDC-193930 (1 a Rh NBD), and CCDC-203770 (1 a Pd) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or firstname.lastname@example.org).
- 13We are grateful to one of the referees for drawing the contrast between the Rh-diphosphane and Rh-diamine-diene catalysts to our attention.
- 142003 and DE-10305943 2003., , , , German Patent DE-10305946,
- 15Accepted theory amongst experts in homogeneous catalysis states that the diene (in this case COD or NBD) are no longer present in the catalyst when it facilitates hydrogenation. But if this were true the catalytic performance of a given organometallic complex would be independent of the initially coordinated diene. This is patently not the case—see Drexler et al.,[15a] where RhI hydrogenation catalysts exhibit a thousand fold difference in reactivities on replacing the COD by NBD. In the critical act of catalysis, possibly even homogeneously, but certainly heterogeneously, under the conditions that we employ, the diene may still be implicated. This is why we have depicted the as-prepared heterogeneous catalyst in Figure 3 a and 3 b;
- 16J. M. Thomas et al., unpublished results.