Correlation between 51V NMR Chemical Shift and Reactivity of Oxovanadium(v) Catalysts for Ethylene Polymerization

Angewandte Chemie - International Edition

Volumn 37, Issue 1-2, 1998, Pages 142-144

  Bühl, Michael ^a  

^a UNIVERSITY OF ZURICH   (Switzerland)

Author keywords

Density functional calculations; Homogeneous catalysis; NMR spectroscopy; Polymerization; Vanadium

Indexed keywords

EID: 0031881685     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(sici)1521-3773(19980202)37:1/2<142::aid-anie142>3.0.co;2-c     Document Type: Article

References (42)

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2. b) W. A. Herrmann, B. Cornils, Angew. Chem. 1997, 109, 1074-1095; Angew. Chem. Int. Ed. Engl. 1997, 36, 1049-1067.
3. b) W. A. Herrmann, B. Cornils, Angew. Chem. 1997, 109, 1074-1095; Angew. Chem. Int. Ed. Engl. 1997, 36, 1049-1067.
4. K. Ziegler, Angew. Chem. 1964, 76, 545-566.
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8. See for example: F. J. Karol, K. J. Cann, B. E. Wagner in Transition Metals and Organometallics as Catalysts for Olefin Polymerization (Eds.: W. Kaminsky, H. Sinn), Springer, New York, 1988, p. 149.
9. F. J. Feher, R. L. Blanski, J. Am. Chem. Soc. 1992, 114, 5886-5887.
10. F. J. Feher, R. L. Blanski, Organometallics 1993, 12, 958-963.
11. M. Bühl, F. A. Hamprecht, J. Comput. Chem., in press.
12. Method for geometry optimization: gradient-corrected exchange-correlation functionals of Becke (A. D. Becke, Phys. Rev. A 1988, 38, 3098-3100) and Perdew (J. P. Perdew, Phys. Rev. B 1986, 33, 8822-8824; ibid. 1986, 34, 7406), denoted BP86, and Basis I, which is Wachters's (14s11p6d)/[8s7p4d] all-electron basis augmented with one additional diffuse d function and two 4p functions for V (A. J. H. Wachters, J. Chem. Phys. 1970, 52, 1033-1036; P. J. Hay, J. Chem. Phys., 1977, 66, 4377-4384), a relativistic 64-electron multi-electron-fit effective core potential together with the (4s4p)/[2s2p] valence double-zeta basis set for Sb (A. Bergner, M. Dolg, W. Küchle, H. Stoll, K. Preuss, Mol. Phys. 1993, 80, 1431-1441: augmented with one d-polarization function, exponent 0.211), and standard 6-31G* basis for all other elements (e.g. W. Hehre, L. Radom, P. von R. Schleyer, J. A. Pople, Ab Initio Molecular Orbital Theory, Wiley, New York, 1986). Zero-point corrections have been computed with harmonic frequencies from analytical or numerical second derivatives. It is known that these types of density functionals afford reliable descriptions of geometries, vibrations, and energetics for transition metal complexes (see, for example, T. Ziegler, Can. J. Chem. 1995, 73, 743-761).
13. Method for geometry optimization: gradient-corrected exchange-correlation functionals of Becke (A. D. Becke, Phys. Rev. A 1988, 38, 3098-3100) and Perdew (J. P. Perdew, Phys. Rev. B 1986, 33, 8822-8824; ibid. 1986, 34, 7406), denoted BP86, and Basis I, which is Wachters's (14s11p6d)/[8s7p4d] all-electron basis augmented with one additional diffuse d function and two 4p functions for V (A. J. H. Wachters, J. Chem. Phys. 1970, 52, 1033-1036; P. J. Hay, J. Chem. Phys., 1977, 66, 4377-4384), a relativistic 64-electron multi-electron-fit effective core potential together with the (4s4p)/[2s2p] valence double-zeta basis set for Sb (A. Bergner, M. Dolg, W. Küchle, H. Stoll, K. Preuss, Mol. Phys. 1993, 80, 1431-1441: augmented with one d-polarization function, exponent 0.211), and standard 6-31G* basis for all other elements (e.g. W. Hehre, L. Radom, P. von R. Schleyer, J. A. Pople, Ab Initio Molecular Orbital Theory, Wiley, New York, 1986). Zero-point corrections have been computed with harmonic frequencies from analytical or numerical second derivatives. It is known that these types of density functionals afford reliable descriptions of geometries, vibrations, and energetics for transition metal complexes (see, for example, T. Ziegler, Can. J. Chem. 1995, 73, 743-761).
14. Method for geometry optimization: gradient-corrected exchange-correlation functionals of Becke (A. D. Becke, Phys. Rev. A 1988, 38, 3098-3100) and Perdew (J. P. Perdew, Phys. Rev. B 1986, 33, 8822-8824; ibid. 1986, 34, 7406), denoted BP86, and Basis I, which is Wachters's (14s11p6d)/[8s7p4d] all-electron basis augmented with one additional diffuse d function and two 4p functions for V (A. J. H. Wachters, J. Chem. Phys. 1970, 52, 1033-1036; P. J. Hay, J. Chem. Phys., 1977, 66, 4377-4384), a relativistic 64-electron multi-electron-fit effective core potential together with the (4s4p)/[2s2p] valence double-zeta basis set for Sb (A. Bergner, M. Dolg, W. Küchle, H. Stoll, K. Preuss, Mol. Phys. 1993, 80, 1431-1441: augmented with one d-polarization function, exponent 0.211), and standard 6-31G* basis for all other elements (e.g. W. Hehre, L. Radom, P. von R. Schleyer, J. A. Pople, Ab Initio Molecular Orbital Theory, Wiley, New York, 1986). Zero-point corrections have been computed with harmonic frequencies from analytical or numerical second derivatives. It is known that these types of density functionals afford reliable descriptions of geometries, vibrations, and energetics for transition metal complexes (see, for example, T. Ziegler, Can. J. Chem. 1995, 73, 743-761).
15. Method for geometry optimization: gradient-corrected exchange-correlation functionals of Becke (A. D. Becke, Phys. Rev. A 1988, 38, 3098-3100) and Perdew (J. P. Perdew, Phys. Rev. B 1986, 33, 8822-8824; ibid. 1986, 34, 7406), denoted BP86, and Basis I, which is Wachters's (14s11p6d)/[8s7p4d] all-electron basis augmented with one additional diffuse d function and two 4p functions for V (A. J. H. Wachters, J. Chem. Phys. 1970, 52, 1033-1036; P. J. Hay, J. Chem. Phys., 1977, 66, 4377-4384), a relativistic 64-electron multi-electron-fit effective core potential together with the (4s4p)/[2s2p] valence double-zeta basis set for Sb (A. Bergner, M. Dolg, W. Küchle, H. Stoll, K. Preuss, Mol. Phys. 1993, 80, 1431-1441: augmented with one d-polarization function, exponent 0.211), and standard 6-31G* basis for all other elements (e.g. W. Hehre, L. Radom, P. von R. Schleyer, J. A. Pople, Ab Initio Molecular Orbital Theory, Wiley, New York, 1986). Zero-point corrections have been computed with harmonic frequencies from analytical or numerical second derivatives. It is known that these types of density functionals afford reliable descriptions of geometries, vibrations, and energetics for transition metal complexes (see, for example, T. Ziegler, Can. J. Chem. 1995, 73, 743-761).
16. Method for geometry optimization: gradient-corrected exchange-correlation functionals of Becke (A. D. Becke, Phys. Rev. A 1988, 38, 3098-3100) and Perdew (J. P. Perdew, Phys. Rev. B 1986, 33, 8822-8824; ibid. 1986, 34, 7406), denoted BP86, and Basis I, which is Wachters's (14s11p6d)/[8s7p4d] all-electron basis augmented with one additional diffuse d function and two 4p functions for V (A. J. H. Wachters, J. Chem. Phys. 1970, 52, 1033-1036; P. J. Hay, J. Chem. Phys., 1977, 66, 4377-4384), a relativistic 64-electron multi-electron-fit effective core potential together with the (4s4p)/[2s2p] valence double-zeta basis set for Sb (A. Bergner, M. Dolg, W. Küchle, H. Stoll, K. Preuss, Mol. Phys. 1993, 80, 1431-1441: augmented with one d-polarization function, exponent 0.211), and standard 6-31G* basis for all other elements (e.g. W. Hehre, L. Radom, P. von R. Schleyer, J. A. Pople, Ab Initio Molecular Orbital Theory, Wiley, New York, 1986). Zero-point corrections have been computed with harmonic frequencies from analytical or numerical second derivatives. It is known that these types of density functionals afford reliable descriptions of geometries, vibrations, and energetics for transition metal complexes (see, for example, T. Ziegler, Can. J. Chem. 1995, 73, 743-761).
17. Method for geometry optimization: gradient-corrected exchange-correlation functionals of Becke (A. D. Becke, Phys. Rev. A 1988, 38, 3098-3100) and Perdew (J. P. Perdew, Phys. Rev. B 1986, 33, 8822-8824; ibid. 1986, 34, 7406), denoted BP86, and Basis I, which is Wachters's (14s11p6d)/[8s7p4d] all-electron basis augmented with one additional diffuse d function and two 4p functions for V (A. J. H. Wachters, J. Chem. Phys. 1970, 52, 1033-1036; P. J. Hay, J. Chem. Phys., 1977, 66, 4377-4384), a relativistic 64-electron multi-electron-fit effective core potential together with the (4s4p)/[2s2p] valence double-zeta basis set for Sb (A. Bergner, M. Dolg, W. Küchle, H. Stoll, K. Preuss, Mol. Phys. 1993, 80, 1431-1441: augmented with one d-polarization function, exponent 0.211), and standard 6-31G* basis for all other elements (e.g. W. Hehre, L. Radom, P. von R. Schleyer, J. A. Pople, Ab Initio Molecular Orbital Theory, Wiley, New York, 1986). Zero-point corrections have been computed with harmonic frequencies from analytical or numerical second derivatives. It is known that these types of density functionals afford reliable descriptions of geometries, vibrations, and energetics for transition metal complexes (see, for example, T. Ziegler, Can. J. Chem. 1995, 73, 743-761).
18. Method for geometry optimization: gradient-corrected exchange-correlation functionals of Becke (A. D. Becke, Phys. Rev. A 1988, 38, 3098-3100) and Perdew (J. P. Perdew, Phys. Rev. B 1986, 33, 8822-8824; ibid. 1986, 34, 7406), denoted BP86, and Basis I, which is Wachters's (14s11p6d)/[8s7p4d] all-electron basis augmented with one additional diffuse d function and two 4p functions for V (A. J. H. Wachters, J. Chem. Phys. 1970, 52, 1033-1036; P. J. Hay, J. Chem. Phys., 1977, 66, 4377-4384), a relativistic 64-electron multi-electron-fit effective core potential together with the (4s4p)/[2s2p] valence double-zeta basis set for Sb (A. Bergner, M. Dolg, W. Küchle, H. Stoll, K. Preuss, Mol. Phys. 1993, 80, 1431-1441: augmented with one d-polarization function, exponent 0.211), and standard 6-31G* basis for all other elements (e.g. W. Hehre, L. Radom, P. von R. Schleyer, J. A. Pople, Ab Initio Molecular Orbital Theory, Wiley, New York, 1986). Zero-point corrections have been computed with harmonic frequencies from analytical or numerical second derivatives. It is known that these types of density functionals afford reliable descriptions of geometries, vibrations, and energetics for transition metal complexes (see, for example, T. Ziegler, Can. J. Chem. 1995, 73, 743-761).
19. Method for geometry optimization: gradient-corrected exchange-correlation functionals of Becke (A. D. Becke, Phys. Rev. A 1988, 38, 3098-3100) and Perdew (J. P. Perdew, Phys. Rev. B 1986, 33, 8822-8824; ibid. 1986, 34, 7406), denoted BP86, and Basis I, which is Wachters's (14s11p6d)/[8s7p4d] all-electron basis augmented with one additional diffuse d function and two 4p functions for V (A. J. H. Wachters, J. Chem. Phys. 1970, 52, 1033-1036; P. J. Hay, J. Chem. Phys., 1977, 66, 4377-4384), a relativistic 64-electron multi-electron-fit effective core potential together with the (4s4p)/[2s2p] valence double-zeta basis set for Sb (A. Bergner, M. Dolg, W. Küchle, H. Stoll, K. Preuss, Mol. Phys. 1993, 80, 1431-1441: augmented with one d-polarization function, exponent 0.211), and standard 6-31G* basis for all other elements (e.g. W. Hehre, L. Radom, P. von R. Schleyer, J. A. Pople, Ab Initio Molecular Orbital Theory, Wiley, New York, 1986). Zero-point corrections have been computed with harmonic frequencies from analytical or numerical second derivatives. It is known that these types of density functionals afford reliable descriptions of geometries, vibrations, and energetics for transition metal complexes (see, for example, T. Ziegler, Can. J. Chem. 1995, 73, 743-761).
20. [8]
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32. For the origin of paramagnetic contributions see, for example: W. Kutzelnigg, U. Fleischer, M. Schindler, in NMR Basic Princ. Prog. 1990, 23, 165-262; an illustration for transition metal complexes can be found in, for example, Y. Ruiz-Morales, G. Schreckenbach, T. Ziegler, J. Phys. Chem. 1996, 100, 3359-3367.
33. See for example: a) P. DeShong, D. R. Sidler, P. J. Rybczynski, A. A. Ogilvie,W. von Philipsborn, J. Org. Chem. 1989, 54, 5432-5437; b) M. Koller, W. von Philipsborn, Organometallics 1992, 11, 467-468; c) M. Koller, Ph.D. Thesis, Universität Zurich, 1993: d) E. J. Meier, W. Kozminski, A. Linden, P. Lustenberger, W. von Philipsborn, Organometallics 1996, 15, 2469-2477.
34. See for example: a) P. DeShong, D. R. Sidler, P. J. Rybczynski, A. A. Ogilvie,W. von Philipsborn, J. Org. Chem. 1989, 54, 5432-5437; b) M. Koller, W. von Philipsborn, Organometallics 1992, 11, 467-468; c) M. Koller, Ph.D. Thesis, Universität Zurich, 1993: d) E. J. Meier, W. Kozminski, A. Linden, P. Lustenberger, W. von Philipsborn, Organometallics 1996, 15, 2469-2477.
35. See for example: a) P. DeShong, D. R. Sidler, P. J. Rybczynski, A. A. Ogilvie,W. von Philipsborn, J. Org. Chem. 1989, 54, 5432-5437; b) M. Koller, W. von Philipsborn, Organometallics 1992, 11, 467-468; c) M. Koller, Ph.D. Thesis, Universität Zurich, 1993: d) E. J. Meier, W. Kozminski, A. Linden, P. Lustenberger, W. von Philipsborn, Organometallics 1996, 15, 2469-2477.
36. See for example: a) P. DeShong, D. R. Sidler, P. J. Rybczynski, A. A. Ogilvie,W. von Philipsborn, J. Org. Chem. 1989, 54, 5432-5437; b) M. Koller, W. von Philipsborn, Organometallics 1992, 11, 467-468; c) M. Koller, Ph.D. Thesis, Universität Zurich, 1993: d) E. J. Meier, W. Kozminski, A. Linden, P. Lustenberger, W. von Philipsborn, Organometallics 1996, 15, 2469-2477.
37. H. Bönnemann, W. Brijoux, R. Brinkmann, W. Meurers, R. Mynott, W. von Philipsborn, T. Egolf, J. Organomet. Chem. 1984, 272, 231-249.
38. R. Fornika, H. Görls, B. Seeman, W. Leitner, J. Chem. Soc. Chem. Commun. 1995, 1479-1480.
39. a) M. Bühl, O. L. Malkina, V. G. Malkin, Helv. Chim. Acta 1996, 79, 742-754;
40. b) M. Bühl, Organometallics 1997, 16, 261-267.
41. No NMR spectra are necessary to order possible cocatalysts according to their Lewis acid strength, but rather to ensure that stable complexes are formed in each case.
42. J. C. W. Chien, A. Razavi, J. Polym. Sci. A 1988, 26, 2369-2380.