Highly active ruthenium catalysts for olefin metathesis: The synergy of N-heterocyclic carbenes and coordinatively labile ligands

Angewandte Chemie - International Edition

Volumn 38, Issue 16, 1999, Pages 2416-2419

  Weskamp, Thomas ^a   Kohl, Florian J ^a   Hieringer, Wolfgang ^a   Gleich, Dieter ^a   Herrmann, Wolfgang A ^a  

^a TECHNICAL UNIVERSITY OF MUNICH   (Germany)

Author keywords

Carbenes; Density functional calculations; Homogeneous catalysis; Metathesis; Ruthenium

Indexed keywords

ALKENE; HETEROCYCLIC COMPOUND; RUTHENIUM;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL REACTION; CHEMICAL STRUCTURE; DISSOCIATION; REACTION ANALYSIS;

EID: 0033549782     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(sici)1521-3773(19990816)38:16<2416::aid-anie2416>3.0.co;2-%23     Document Type: Article

References (36)

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21. The DZVP basis set (N. Godbout, D. R. Salahub, J. Andzelm, E. Wimmer, Can. J. Chem. 1992, 70, 560) was chosen for all calculations. This basis set, together with the A1 set of auxiliary fitting functions for the density as well as for the exchange-correlation potential, is optimized especially for DFT calculations to reduce the basis set superposition error. Since relativistic effects are modest for the late second-row transition metals (J. Li, G. Schreckenbach, T. Ziegler, J. Am. Chem. Soc. 1995, 117, 486) a pseudopotential for the Ru atom is not necessary. All structures were optimized without any restrictions by using the BP86 functional (A. D. Becke, Phys. Rev. A 1988, 38, 3098; J. P. Perdew, Phys. Rev. B 1986, 33, 8822), which has proven to be adequate for the calculation of bond dissociation energies (see for example: R. Schmid, W. A. Herrmann, G. Frenking, Organometallics 1997, 16, 701; A. W. Ehlers, Y. Ruizmorales, E. J. Baerends, T. Ziegler, Inorg. Chem. 1997, 36, 5031). The resulting geometries were verified to be true minima by frequency calculations. Dissociation energies include zero-point vibrational correction. All calculations were performed with the program DGauss (DGauss, Release 4.0, Oxford Molecular, 1998).
22. The DZVP basis set (N. Godbout, D. R. Salahub, J. Andzelm, E. Wimmer, Can. J. Chem. 1992, 70, 560) was chosen for all calculations. This basis set, together with the A1 set of auxiliary fitting functions for the density as well as for the exchange-correlation potential, is optimized especially for DFT calculations to reduce the basis set superposition error. Since relativistic effects are modest for the late second-row transition metals (J. Li, G. Schreckenbach, T. Ziegler, J. Am. Chem. Soc. 1995, 117, 486) a pseudopotential for the Ru atom is not necessary. All structures were optimized without any restrictions by using the BP86 functional (A. D. Becke, Phys. Rev. A 1988, 38, 3098; J. P. Perdew, Phys. Rev. B 1986, 33, 8822), which has proven to be adequate for the calculation of bond dissociation energies (see for example: R. Schmid, W. A. Herrmann, G. Frenking, Organometallics 1997, 16, 701; A. W. Ehlers, Y. Ruizmorales, E. J. Baerends, T. Ziegler, Inorg. Chem. 1997, 36, 5031). The resulting geometries were verified to be true minima by frequency calculations. Dissociation energies include zero-point vibrational correction. All calculations were performed with the program DGauss (DGauss, Release 4.0, Oxford Molecular, 1998).
23. The DZVP basis set (N. Godbout, D. R. Salahub, J. Andzelm, E. Wimmer, Can. J. Chem. 1992, 70, 560) was chosen for all calculations. This basis set, together with the A1 set of auxiliary fitting functions for the density as well as for the exchange-correlation potential, is optimized especially for DFT calculations to reduce the basis set superposition error. Since relativistic effects are modest for the late second-row transition metals (J. Li, G. Schreckenbach, T. Ziegler, J. Am. Chem. Soc. 1995, 117, 486) a pseudopotential for the Ru atom is not necessary. All structures were optimized without any restrictions by using the BP86 functional (A. D. Becke, Phys. Rev. A 1988, 38, 3098; J. P. Perdew, Phys. Rev. B 1986, 33, 8822), which has proven to be adequate for the calculation of bond dissociation energies (see for example: R. Schmid, W. A. Herrmann, G. Frenking, Organometallics 1997, 16, 701; A. W. Ehlers, Y. Ruizmorales, E. J. Baerends, T. Ziegler, Inorg. Chem. 1997, 36, 5031). The resulting geometries were verified to be true minima by frequency calculations. Dissociation energies include zero-point vibrational correction. All calculations were performed with the program DGauss (DGauss, Release 4.0, Oxford Molecular, 1998).
24. The DZVP basis set (N. Godbout, D. R. Salahub, J. Andzelm, E. Wimmer, Can. J. Chem. 1992, 70, 560) was chosen for all calculations. This basis set, together with the A1 set of auxiliary fitting functions for the density as well as for the exchange-correlation potential, is optimized especially for DFT calculations to reduce the basis set superposition error. Since relativistic effects are modest for the late second-row transition metals (J. Li, G. Schreckenbach, T. Ziegler, J. Am. Chem. Soc. 1995, 117, 486) a pseudopotential for the Ru atom is not necessary. All structures were optimized without any restrictions by using the BP86 functional (A. D. Becke, Phys. Rev. A 1988, 38, 3098; J. P. Perdew, Phys. Rev. B 1986, 33, 8822), which has proven to be adequate for the calculation of bond dissociation energies (see for example: R. Schmid, W. A. Herrmann, G. Frenking, Organometallics 1997, 16, 701; A. W. Ehlers, Y. Ruizmorales, E. J. Baerends, T. Ziegler, Inorg. Chem. 1997, 36, 5031). The resulting geometries were verified to be true minima by frequency calculations. Dissociation energies include zero-point vibrational correction. All calculations were performed with the program DGauss (DGauss, Release 4.0, Oxford Molecular, 1998).
25. The DZVP basis set (N. Godbout, D. R. Salahub, J. Andzelm, E. Wimmer, Can. J. Chem. 1992, 70, 560) was chosen for all calculations. This basis set, together with the A1 set of auxiliary fitting functions for the density as well as for the exchange-correlation potential, is optimized especially for DFT calculations to reduce the basis set superposition error. Since relativistic effects are modest for the late second-row transition metals (J. Li, G. Schreckenbach, T. Ziegler, J. Am. Chem. Soc. 1995, 117, 486) a pseudopotential for the Ru atom is not necessary. All structures were optimized without any restrictions by using the BP86 functional (A. D. Becke, Phys. Rev. A 1988, 38, 3098; J. P. Perdew, Phys. Rev. B 1986, 33, 8822), which has proven to be adequate for the calculation of bond dissociation energies (see for example: R. Schmid, W. A. Herrmann, G. Frenking, Organometallics 1997, 16, 701; A. W. Ehlers, Y. Ruizmorales, E. J. Baerends, T. Ziegler, Inorg. Chem. 1997, 36, 5031). The resulting geometries were verified to be true minima by frequency calculations. Dissociation energies include zero-point vibrational correction. All calculations were performed with the program DGauss (DGauss, Release 4.0, Oxford Molecular, 1998).
26. The DZVP basis set (N. Godbout, D. R. Salahub, J. Andzelm, E. Wimmer, Can. J. Chem. 1992, 70, 560) was chosen for all calculations. This basis set, together with the A1 set of auxiliary fitting functions for the density as well as for the exchange-correlation potential, is optimized especially for DFT calculations to reduce the basis set superposition error. Since relativistic effects are modest for the late second-row transition metals (J. Li, G. Schreckenbach, T. Ziegler, J. Am. Chem. Soc. 1995, 117, 486) a pseudopotential for the Ru atom is not necessary. All structures were optimized without any restrictions by using the BP86 functional (A. D. Becke, Phys. Rev. A 1988, 38, 3098; J. P. Perdew, Phys. Rev. B 1986, 33, 8822), which has proven to be adequate for the calculation of bond dissociation energies (see for example: R. Schmid, W. A. Herrmann, G. Frenking, Organometallics 1997, 16, 701; A. W. Ehlers, Y. Ruizmorales, E. J. Baerends, T. Ziegler, Inorg. Chem. 1997, 36, 5031). The resulting geometries were verified to be true minima by frequency calculations. Dissociation energies include zero-point vibrational correction. All calculations were performed with the program DGauss (DGauss, Release 4.0, Oxford Molecular, 1998).
27. Only the trans arrangement of the two neutral ligands has been considered since it is more stable for electronic as well as steric reasons; see also S. M. Hansen, F. Rominger, M. Metz, P. Hofmann, Chem. Eur. J. 1999, 5, 557-566.
28. -1, respectively.
29. In the course of the editing of this manuscript two publications of a similar complex appeared: a) J. Huang, E. D. Stevens, S. P. Nolan, J. L. Petersen, J. Am. Chem. Soc. 1999, 121, 2674-2678; b) M. Scholl, T. M. Trnka, J. P. Morgan, R. H. Grubbs, Tetrahedron Lett. 1999, 40, 2247-2250.
30. In the course of the editing of this manuscript two publications of a similar complex appeared: a) J. Huang, E. D. Stevens, S. P. Nolan, J. L. Petersen, J. Am. Chem. Soc. 1999, 121, 2674-2678; b) M. Scholl, T. M. Trnka, J. P. Morgan, R. H. Grubbs, Tetrahedron Lett. 1999, 40, 2247-2250.
31. E. L. Dias, R. H. Grubbs, Organometallics 1998, 17, 2758-2767.
32. The different trans influences of phosphane and NHC ligands on the dissociation [Eq. (2)] were not considered in this study.
33. U. Frenzel, T. Weskamp, F. J. Kohl, W. C. Schattenmann, O. Nuyken, W. A. Herrmann, J. Organomet. Chem. 1999, 586, 263-265.
34. L. Ackermann, A. Fürstner, T. Weskamp, F. J. Kohl, W. A. Herrmann, Tetrahedron Lett. 1999, 40, 4787-4790.
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