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    Crystallographic 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 (or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or
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  • 13
    We are grateful to one of the referees for drawing the contrast between the Rh-diphosphane and Rh-diamine-diene catalysts to our attention.
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    Accepted 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.[13] This is why we have depicted the as-prepared heterogeneous catalyst in Figure 3 a and 3 b;
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    J. M. Thomas et al., unpublished results.
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