Mechanistic insight into the polymerization of butadiene by "ligand-free" polybutadienyl-nickel(II) complexes: Computational assignment of the true structure of the resting state

Organometallics

Volumn 27, Issue 10, 2008, Pages 2159-2162

  Tobisch, Sven ^a   Taube, Rudolf ^b  

^a UNIVERSITY OF ST ANDREWS   (United Kingdom)

^b NONE   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

BUTADIENE; CHEMICAL REACTIONS; LIGANDS; NICKEL; NICKEL ALLOYS; NICKEL COMPOUNDS; POLYMERIZATION; POLYMERS; SULFUR COMPOUNDS;

AMERICAN CHEMICAL SOCIETY (ACS); CATALYST RESTING STATE; CHAIN GROWTH; DFT CALCULATIONS; LIGAND FREE; NICKEL (IMIDAZOLE) COMPLEXES;

MONOMERS;

EID: 44649123603     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om701214u     Document Type: Article

References (38)

1. Durand, J. P.; Dawans, F.; Teyssie, P. J. Polym. Sci., Part A 1970, 8, 979.
2. Porri, L.; Giarrusso, A.; Ricci, G. Prog. Polym. Sci. 1991, 16, 405.
3. Taube, R.; Sylvester, G. In Applied Homogeneous Catalysis with Organometallic Complexes; Cornils, B., Herrmann, W. A., Eds.; VCH: Weinheim, Germany, 1996, pp 280-318..
4. Thiele, S. K.-H.; Wilson, D. R. J. Macromol. Sci., Part C: Polym. Rev. 2003, C43, 581.
5. Kormer, V. A.; Babitskii, B. D.; Lobach, M. I. Adv. Chem. Ser. 1969, 91, 306.
6. Harrod, J. F.; Wallace, L. R. Macromolecules 1969, 2, 449.
7. Dolgoplosk, B. A. Sov. Sci. Rev., Sect. B 1980, 2, 203.
8. Hadjiandeou, P.; Julemont, M.; Teyssie, M. Macromolecules 1984, 17, 2455.
9. Taube, R.; Schmidt, U. Z. Chem. 1977, 17, 349.
10. (a) Taube, R.; Böhme, P.; Gehrke, J.-P. J. Organomet. Chem. 1990, 399, 327.
11. (b) Taube, R.; Gehrke, J.-P.; Böhme, P.; Scherzer, K. J. Organomet. Chem. 1991, 410, 403.
12. (c) Taube, R.; Wache, S. J. Organomet. Chem. 1992, 428, 431.
13. (d) Taube, R.; Langlotz, J. Makromol. Chem. 1993, 194, 705.
14. (e) Taube, R.; Wache, S.; Sieler, J.; Kempe, R. J. Organomet. Chem. 1993, 456, 131.
15. (f) Wache, S.; Taube, R. J. Organomet. Chem. 1993, 456, 137.
16. (g) Taube, R.; Wache, S.; Kehlen, H. J. Mol. Catal. A: Chem. 1995, 97, 21.
17. (h) Taube, R.; Langlotz, J.; Sieler, J.; Gelbrich, Th.; Tittes; K, J. Organomet. Chem. 2000, 597, 92.
18. 10c
19. The curved lines in syn-B and anti-B indicate some uncertainty regarding which of the double bonds of the polybutadienyl chain actually coordinate at the Ni center. The reversible arrows connecting syn-lanti-B and syn-lanti-C describe the existing equilibrium, without elaborating further on its kinetics.
20. (a) Tobisch, S.; Taube, R. Organometallics 1999, 18, 5204.
21. (b) Tobisch, S. Acc. Chem. Res. 2002, 35, 96.
22. O'Connor, A. R.; White, P. S.; Brookhart, M. J. Am. Chem. Soc. 2007, 129, 4142.
23. Tao, J.; Perdew, J. P.; Staroverov, V. N.; Scuseria, G. E. Phys. Rev. Lett. 2003, 91, 146401.
24. Andrae, D.; Häussermann, U.; Dolg, M.; Stoll, H.; Preuss, H. Theor. Chim. Acta 1990, 77, 123.
25. Schäfer, A.; Huber, C.; Ahlrichs, R. J. Chem. Phys. 1994, 100, 5829.
26. Calculations employed TURBOMOLE V5.8 and used the TPSS functional together with flexible basis sets of valence triple-ζ quality. See the Supporting Information for full details.
27. See the Supporting Information for further details.
28. Tobisch, S.; Taube, R. Organometallics 1999, 18, 3045.
29. This transforms into a relative likelihood of ∼0.1:100 (298 K) for 1,2- and cis-1,4-insertion events.
30. (a) London, F. J. Phys. Radium 1937, 8, 397.
31. (b) Ditchfield, R. Mol. Phys. 1974, 27, 789.
32. (c) Wolinski, K.; Hinton, J. F.; Pulay, P. J. Am. Chem. Soc. 1990, 112, 8251.
33. (d) Ruud, K.; Helgaker, T.; Bak, K. L.; Jørgenen, P.; Jensen, H. J. A. J. Chem. Phys. 1993, 99, 3897.
34. (e) Helgaker, T.; Watson, M.; Handy, N. C. J. Chem. Phys. 2000, 113, 9402.
35. Frisch, M. J.; et al. Gaussian 03, Rev. B.05; Gaussian, Inc., Pittsburgh, PA, 2003.
36. Kaupp, M.; Bühl, M.; Malkin, V. G. Calculation of NMR and EPR Parameters: Theory and Applications; Wiley-VCH: Weinheim, Germany, 2004.
37. This transforms into a relative acceleration by a factor of ∼10.
38. -1 by taking the reaction conditions as reported in ref 10g into account