The first grubbs-type metathesis catalyst with cis stereochemistry: Synthesis of [(n2-dtbpm)Cl2Ru=CH-CH=CMe2] from a novel, coordinatively unsaturated dinuclear ruthenium dihydride

Chemistry - A European Journal

Volumn 5, Issue 2, 1999, Pages 557-566

  Hansen, Sven Michael ^a   Rominger, Frank ^a   Metz, Markus ^a   Hofmann, Peter ^a  

^a UNIVERSITY OF HEIDELBERG   (Germany)

Author keywords

Ab initio calculations; Carbene complexes; Hydrido complexes; Metathesis; Ruthenium

Indexed keywords

RUTHENIUM DERIVATIVE;

ARTICLE; CATALYST; CHEMICAL ANALYSIS; CHEMICAL REACTION; COMPLEX FORMATION; STEREOCHEMISTRY; SYNTHESIS; X RAY DIFFRACTION;

EID: 0033007369     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3765(19990201)5:2<557::AID-CHEM557>3.0.CO;2-A     Document Type: Article

References (67)

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34. ii Ru(5p) = -5.47 eV (ξ= 2.043).
35. ii Ru(5p) = -5.47 eV (ξ= 2.043).
36. ii Ru(5p) = -5.47 eV (ξ= 2.043).
37. ii Ru(5p) = -5.47 eV (ξ= 2.043).
38. ii Ru(5p) = -5.47 eV (ξ= 2.043).
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40. For the DFT calculations the empirically parametrized B3LYP method within the Gaussian 94 (Revision E.2) package was used: M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. A. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. R. Stefanov, A. Nanayakkara, M. Challacombe, C. Y. Peng, P. Y. Ayala, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzales, J. A. Pople, Gaussian Inc., Pittsburgh PA, 1995. methodology: A. D. Becke, Phys. Rev. 1988, A38, 3098-3100; C. Lee, W. Yang, R. G. Parr, Phys. Rev. 1988, B37, 785-798; S. H. Vosko, L. Wilk, M. Nusair, Can. J. Phys. 1980, 58, 1200-1211. All geometries were optimized with the LANL2DZ basis set: P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 299-310; P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 284-298; T. H. Dunning, P. J. Hay in Modern Theoretical Chemistry (Ed.: H. F. Schaefer III), Plenum, New York, 1976, 1-27.
41. For the DFT calculations the empirically parametrized B3LYP method within the Gaussian 94 (Revision E.2) package was used: M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. A. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. R. Stefanov, A. Nanayakkara, M. Challacombe, C. Y. Peng, P. Y. Ayala, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzales, J. A. Pople, Gaussian Inc., Pittsburgh PA, 1995. methodology: A. D. Becke, Phys. Rev. 1988, A38, 3098-3100; C. Lee, W. Yang, R. G. Parr, Phys. Rev. 1988, B37, 785-798; S. H. Vosko, L. Wilk, M. Nusair, Can. J. Phys. 1980, 58, 1200-1211. All geometries were optimized with the LANL2DZ basis set: P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 299-310; P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 284-298; T. H. Dunning, P. J. Hay in Modern Theoretical Chemistry (Ed.: H. F. Schaefer III), Plenum, New York, 1976, 1-27.
42. For the DFT calculations the empirically parametrized B3LYP method within the Gaussian 94 (Revision E.2) package was used: M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. A. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. R. Stefanov, A. Nanayakkara, M. Challacombe, C. Y. Peng, P. Y. Ayala, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzales, J. A. Pople, Gaussian Inc., Pittsburgh PA, 1995. methodology: A. D. Becke, Phys. Rev. 1988, A38, 3098-3100; C. Lee, W. Yang, R. G. Parr, Phys. Rev. 1988, B37, 785-798; S. H. Vosko, L. Wilk, M. Nusair, Can. J. Phys. 1980, 58, 1200-1211. All geometries were optimized with the LANL2DZ basis set: P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 299-310; P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 284-298; T. H. Dunning, P. J. Hay in Modern Theoretical Chemistry (Ed.: H. F. Schaefer III), Plenum, New York, 1976, 1-27.
43. For the DFT calculations the empirically parametrized B3LYP method within the Gaussian 94 (Revision E.2) package was used: M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. A. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. R. Stefanov, A. Nanayakkara, M. Challacombe, C. Y. Peng, P. Y. Ayala, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzales, J. A. Pople, Gaussian Inc., Pittsburgh PA, 1995. methodology: A. D. Becke, Phys. Rev. 1988, A38, 3098-3100; C. Lee, W. Yang, R. G. Parr, Phys. Rev. 1988, B37, 785-798; S. H. Vosko, L. Wilk, M. Nusair, Can. J. Phys. 1980, 58, 1200-1211. All geometries were optimized with the LANL2DZ basis set: P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 299-310; P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 284-298; T. H. Dunning, P. J. Hay in Modern Theoretical Chemistry (Ed.: H. F. Schaefer III), Plenum, New York, 1976, 1-27.
44. For the DFT calculations the empirically parametrized B3LYP method within the Gaussian 94 (Revision E.2) package was used: M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. A. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. R. Stefanov, A. Nanayakkara, M. Challacombe, C. Y. Peng, P. Y. Ayala, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzales, J. A. Pople, Gaussian Inc., Pittsburgh PA, 1995. methodology: A. D. Becke, Phys. Rev. 1988, A38, 3098-3100; C. Lee, W. Yang, R. G. Parr, Phys. Rev. 1988, B37, 785-798; S. H. Vosko, L. Wilk, M. Nusair, Can. J. Phys. 1980, 58, 1200-1211. All geometries were optimized with the LANL2DZ basis set: P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 299-310; P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 284-298; T. H. Dunning, P. J. Hay in Modern Theoretical Chemistry (Ed.: H. F. Schaefer III), Plenum, New York, 1976, 1-27.
45. For the DFT calculations the empirically parametrized B3LYP method within the Gaussian 94 (Revision E.2) package was used: M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. A. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. R. Stefanov, A. Nanayakkara, M. Challacombe, C. Y. Peng, P. Y. Ayala, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzales, J. A. Pople, Gaussian Inc., Pittsburgh PA, 1995. methodology: A. D. Becke, Phys. Rev. 1988, A38, 3098-3100; C. Lee, W. Yang, R. G. Parr, Phys. Rev. 1988, B37, 785-798; S. H. Vosko, L. Wilk, M. Nusair, Can. J. Phys. 1980, 58, 1200-1211. All geometries were optimized with the LANL2DZ basis set: P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 299-310; P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 284-298; T. H. Dunning, P. J. Hay in Modern Theoretical Chemistry (Ed.: H. F. Schaefer III), Plenum, New York, 1976, 1-27.
46. For the DFT calculations the empirically parametrized B3LYP method within the Gaussian 94 (Revision E.2) package was used: M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. A. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. R. Stefanov, A. Nanayakkara, M. Challacombe, C. Y. Peng, P. Y. Ayala, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzales, J. A. Pople, Gaussian Inc., Pittsburgh PA, 1995. methodology: A. D. Becke, Phys. Rev. 1988, A38, 3098-3100; C. Lee, W. Yang, R. G. Parr, Phys. Rev. 1988, B37, 785-798; S. H. Vosko, L. Wilk, M. Nusair, Can. J. Phys. 1980, 58, 1200-1211. All geometries were optimized with the LANL2DZ basis set: P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 299-310; P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 284-298; T. H. Dunning, P. J. Hay in Modern Theoretical Chemistry (Ed.: H. F. Schaefer III), Plenum, New York, 1976, 1-27.
47. No imaginary frequencies were found for these stationary points.
48. In these calculations a large 6-311 + G(2d,2p) basis set was used for the main group atoms. The ruthenium basis for the Hay and Wadt ECP was expanded by uncontracting one s, one p, and one d function and by adding a diffuse d function and two f functions contracted from three primitive f functions.
49. 2 group is parallel to the Cl-Ru-Cl axis in 3 and interacts with the metal d orbital which is most strongly destabilized by the π-donor Cl ligands. In 4 it is parallel to the more strongly bent P1-Ru-Cl1 axis.
50. [19a] Accordingly, different orientations are observed in crystal structures for a variety of trans complexes. Such low rotational barriers render questionable all mechanistic arguments in olefin metathesis that are based upon specific carbene orientations.
51. a) P. Hofmann, C. Meier, U. Englert, M. U. Schmidt, Chem. Ber. 1992, 125, 353-365;
52. b) P. Hofmann, G. Unfried, Chem. Ber. 1992, 125, 659-661;
53. c) P. Hofmann, L. A. Perez-Moya, O. Steigelmann, J. Riede, Organometallics 1992, 11, 1167-1176;
54. d) P. Hofmann, C. Meier, W. Hiller, M. Heckel, J. Riede, M. U. Schmidt, J. Organomet. Chem. 1995, 490, 51-70. In spite of a P-C-P angle close to 120° for the free ligand (X-ray diffraction: P. Hofmann, I. Gruber, F. Rominger, unpublished results), dtbpm prefers four-membered chelate ring coordination to single metal centers due to the gem-dialkyl effect. The first ionization potential of dtbpm is only 7.7 eV (UV PES: P. Hofmann, P. Bischof, R. Gleiter, unpublished results).
55. d) P. Hofmann, C. Meier, W. Hiller, M. Heckel, J. Riede, M. U. Schmidt, J. Organomet. Chem. 1995, 490, 51-70. In spite of a P-C-P angle close to 120° for the free ligand (X-ray diffraction: P. Hofmann, I. Gruber, F. Rominger, unpublished results), dtbpm prefers four-membered chelate ring coordination to single metal centers due to the gem-dialkyl effect. The first ionization potential of dtbpm is only 7.7 eV (UV PES: P. Hofmann, P. Bischof, R. Gleiter, unpublished results).
56. d) P. Hofmann, C. Meier, W. Hiller, M. Heckel, J. Riede, M. U. Schmidt, J. Organomet. Chem. 1995, 490, 51-70. In spite of a P-C-P angle close to 120° for the free ligand (X-ray diffraction: P. Hofmann, I. Gruber, F. Rominger, unpublished results), dtbpm prefers four-membered chelate ring coordination to single metal centers due to the gem-dialkyl effect. The first ionization potential of dtbpm is only 7.7 eV (UV PES: P. Hofmann, P. Bischof, R. Gleiter, unpublished results).
57. S. M. Hansen, P. Hofmann, unpublished results.
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60. As one referee pointed out, the entire mechanistic picture elaborated by Grubbs et al. might need revision in this case.
61. -3. The two hydrido ligands of 8 are terminal, and we tentatively assign them to the two exo positions indicated in Scheme 2, although other static or dynamic disorder cannot be excluded with certainty at this point (see text).
62. -3;
63. 3. Crystallographic data (excluding structure factors) for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publications no. CCDC-101932 (8), CCDC-101931 (2), and CCDC-103028 (7). Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB21EZ, UK (fax: (+44)1223-336-033; e-mail: deposit@ccdc.cam.ac.uk).
64. [27a] dissociatiate in solution according to molecular weight determinations (Signer method).
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