C-H bonds are not elongated by coordination to lanthanide metals: Single-crystal neutron diffraction structures of (C5Me5)Y(OC6H3(t)Bu2)CH(SiMe3)2 at 20 K and (C5Me5)La{CH(SiMe3)2}2 at 15 K [2]

Journal of the American Chemical Society

Volumn 121, Issue 6, 1999, Pages 1381-1382

  Klooster, Wim T ^a   Brammer, Lee ^b   Schaverien, Colin J ^c   Budzelaar, Peter H M ^d  

^a BROOKHAVEN NATIONAL LABORATORY   (United States)

^b UNIVERSITY OF MISSOURI ST LOUIS   (United States)

^c SHELL RESEARCH AND TECHNOLOGY CENTRE   (Netherlands)

^d RADBOUD UNIVERSITY NIJMEGEN   (Netherlands)

Author keywords

[No Author keywords available]

Indexed keywords

CARBON; HYDROGEN;

CHEMICAL STRUCTURE; CRYSTAL; LETTER; NEUTRON; X RAY DIFFRACTION;

EID: 0033576973     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja983068b     Document Type: Letter

References (32)

1. Schaverien, C. J. Adv. Organomet. Chem. 1994, 36, 283. Edelmann, F. T. (Chapter 2); Chirik, P. J.; Bercaw, J. E. (Chapter 3). In Metallocenes: Synthesis, Reactivity, Applications: Togni, A., Halterman, R. L., Eds.; Wiley- VCH: New York/1998; Vol. 1.
2. Schaverien, C. J. Adv. Organomet. Chem. 1994, 36, 283. Edelmann, F. T. (Chapter 2); Chirik, P. J.; Bercaw, J. E. (Chapter 3). In Metallocenes: Synthesis, Reactivity, Applications: Togni, A., Halterman, R. L., Eds.; Wiley-VCH: New York/1998; Vol. 1.
3. (a) Jeske, G.; Lauke, H.; Mauermann, H.; Swepston, P. N.; Schumann, H.; Marks, T. J. J. Am. Chem. Soc. 1985, 107, 8091.
4. (b) Jeske, G.; Schock, L. E.; Swepston, P. N.; Schumann, H.; Marks, T. J. J. Am. Chem. Soc. 1985, 107, 8103.
5. (c) Heeres, H. J.; Meetsma, A.; Teuben, J. H.; Rogers, R. D. Organometallics 1989, 9, 2637
6. (d) Schumann, H.; Esser, L.; Loebel, J.; Dietrich, A.; Van der Helm, D.; Ji, X. Organometallics 1991, 10, 2585
7. 2h) suffered from disorder problems or details of the γ-methyl group were not reported,
8. (f) Den Haan, K. H.; De Boer, J. L.; Teuben, J. H.; Spek, A. L.; Kojic-Prodic, B.; Hays, G. R.; Huis, R. Organometallics 1986, 5, 1726.
9. (g) Heeres, H. J.; Renkema, J.; Booij, M.; Meetsma, A.; Teuben, J. H. Organometallics 1988, 7, 2495.
10. (h) Hitchcock, P. B.; Lappert, M. F.; Smith, R. G.; Barlett, R. A.; Power, P. P. J. Chem. Soc., Chem. Commun. 1988, 1007
11. (i) Giardello, M. A.; Conticello, V. P.; Brard, L.; Sabat, M.; Rheingold, A. L.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1994, 116, 10212.
12. Brookhart, M.; Green, M. L. H.; Wong, L.-L. Prog. Inorg. Chem. 1988, 36, 1.
13. Schaverien, C. J. Organometallics 1994, 13, 69.
14. Van der Heijden, H.; Schavenen, C. J.; Orpen, A. G. Organometallics 1989, 8, 255.
15. Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1988, 110, 108.
16. 2) 1.064 for all 8852 data. For details of the X-ray structure determination of 1 at 128 K see the Supporting Information.
17. 2) 1.289 for all 4616 data.
18. 3
19. For a strong agostic interaction one would expect an elongation of 0.03-0.05 Å. The random errors in the C-H bond lengths are on the order of 0.007 Å for 1 and 0.02 Å for 2.
20. Program ADF (Baerends, E. J.; Ellis, D. E.; Ros, P. Chem. Phys. 1973, 2, 41. Versluis, L.; Ziegler, T. H. Chem. Phys. 1988, 88, 322. te Velde, G.; Baerends, E. J. J. Comput. Chem. 1992, 99, 84. Boerrigter, P. M.; te Velde, G.; Baerends, E. J. Int. J. Quantum Chem. 1988, 33, 87) using quasi-relativistic frozen cores (Boerrigter, P. M. Ph.D. Thesis, Free University, Amsterdam, 1987. Ziegler, T.; Tschinke, V.; Baerends, E. J.; Snijders, J. G.; Ravenek, W. J. Phys. Chem. 1989, 93, 3050). For further details see Supporting Information.
21. Program ADF (Baerends, E. J.; Ellis, D. E.; Ros, P. Chem. Phys. 1973, 2, 41. Versluis, L.; Ziegler, T. H. Chem. Phys. 1988, 88, 322. te Velde, G.; Baerends, E. J. J. Comput. Chem. 1992, 99, 84. Boerrigter, P. M.; te Velde, G.; Baerends, E. J. Int. J. Quantum Chem. 1988, 33, 87) using quasi-relativistic frozen cores (Boerrigter, P. M. Ph.D. Thesis, Free University, Amsterdam, 1987. Ziegler, T.; Tschinke, V.; Baerends, E. J.; Snijders, J. G.; Ravenek, W. J. Phys. Chem. 1989, 93, 3050). For further details see Supporting Information.
22. Program ADF (Baerends, E. J.; Ellis, D. E.; Ros, P. Chem. Phys. 1973, 2, 41. Versluis, L.; Ziegler, T. H. Chem. Phys. 1988, 88, 322. te Velde, G.; Baerends, E. J. J. Comput. Chem. 1992, 99, 84. Boerrigter, P. M.; te Velde, G.; Baerends, E. J. Int. J. Quantum Chem. 1988, 33, 87) using quasi-relativistic frozen cores (Boerrigter, P. M. Ph.D. Thesis, Free University, Amsterdam, 1987. Ziegler, T.; Tschinke, V.; Baerends, E. J.; Snijders, J. G.; Ravenek, W. J. Phys. Chem. 1989, 93, 3050). For further details see Supporting Information.
23. Program ADF (Baerends, E. J.; Ellis, D. E.; Ros, P. Chem. Phys. 1973, 2, 41. Versluis, L.; Ziegler, T. H. Chem. Phys. 1988, 88, 322. te Velde, G.; Baerends, E. J. J. Comput. Chem. 1992, 99, 84. Boerrigter, P. M.; te Velde, G.; Baerends, E. J. Int. J. Quantum Chem. 1988, 33, 87) using quasi-relativistic frozen cores (Boerrigter, P. M. Ph.D. Thesis, Free University, Amsterdam, 1987. Ziegler, T.; Tschinke, V.; Baerends, E. J.; Snijders, J. G.; Ravenek, W. J. Phys. Chem. 1989, 93, 3050). For further details see Supporting Information.
24. Program ADF (Baerends, E. J.; Ellis, D. E.; Ros, P. Chem. Phys. 1973, 2, 41. Versluis, L.; Ziegler, T. H. Chem. Phys. 1988, 88, 322. te Velde, G.; Baerends, E. J. J. Comput. Chem. 1992, 99, 84. Boerrigter, P. M.; te Velde, G.; Baerends, E. J. Int. J. Quantum Chem. 1988, 33, 87) using quasi-relativistic frozen cores (Boerrigter, P. M. Ph.D. Thesis, Free University, Amsterdam, 1987. Ziegler, T.; Tschinke, V.; Baerends, E. J.; Snijders, J. G.; Ravenek, W. J. Phys. Chem. 1989, 93, 3050). For further details see Supporting Information.
25. 2.
26. The Cα-Siβ bonds are not significantly elongated.
27. +. Horton, A. D.; Orpen, A. G. Organometallics 1991, 10, 3910.
28. +. Horton, A. D.; Orpen, A. G. Organometallics 1991, 10, 3910.
29. 5
30. 2 also provided little evidence for α-agostic interactions. Hitchcock, P. B.; Howard, J. A. K.; Lappert, M. F.; Leung, W.-P.; Mason, S. A. J. Chem. Soc., Chem. Commun. 1990, 847.
31. γ-H angles in the agostic methyl groups of 2 reveal that they, in contrast to all their nonagostic Si-Me counterparts, are distorted, i.e., Si(2)-C(17)-H(17a,b,c) = 112.3(10)°, 107,4(12)°, 117.7-(12)° (in 3: 114.93°, 108.29°, 114.79°) and Si(4)-C(22)-H(22a,b,c) = 114.9-(11)°, 109.7(15)°, 113.7(12)° (in 3: 115.03°, 109.49°, 112.46°).
32. See Suppporting Information.