Reductive activation of tripod metal compounds: Identification of intermediates and preparative application

European Journal of Inorganic Chemistry

Volumn , Issue 9, 2008, Pages 1413-1422

  Mautz, Jürgen ^a   Heinze, Katja ^a   Wadepohl, Hubert ^a   Huttner, Gottfried ^a  

^a UNIVERSITY OF HEIDELBERG   (Germany)

Author keywords

Cobalt; Nickel; Oxidative addition; Reductive activation; Silicon hydrides; Tin hydrides; Tripodal ligands

Indexed keywords

ATOMS; BROMINE COMPOUNDS; COBALT; COBALT COMPOUNDS; HYDROGEN; LIGANDS; NICKEL; NICKEL COMPOUNDS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; SILANES; TIN COMPOUNDS; X RAY ANALYSIS;

ARGON ATMOSPHERES; COORDINATION GEOMETRY; HETEROELEMENTS; OXIDATION STATE; OXIDATIVE ADDITIONS; REACTIVE SPECIES; REDUCTIVE ACTIVATION; SOLID-STATE STRUCTURES; STANNANE; TRIPODAL LIGANDS;

CHEMICAL ACTIVATION;

EID: 53349180260     PISSN: 14341948     EISSN: 10990682     Source Type: Journal    
DOI: 10.1002/ejic.200700873     Document Type: Article

References (32)

1. a) L. Sacconi, F. Mani in Transition Metal Chemistry, (Eds: G. A. Melson, B. N. Figgis), Marcel Decker, New York, 1982, vol. 8, p. 179;
2. b) D. A. Buckingham, C. R. Clark in Comprehensive Coordination Chemistry (Eds.: S. G. Wilkinson, R. D. Guillard, J. A. McCleverty), Pergamon, New York, 1987, vol. 4, p. 635;
3. c) L. Sacconi, F. Mani, A. Bencini in Comprehensive Coordination Chemistry (Eds.: S. G. Wilkinson, R. D. Guillard, J. A. McCleverty), Pergamon, New York, 1987, vol. 5, p. 1.
4. F. Cecconi, C. A. Ghilardi, S. Midollini, S. Moneti, A. Orlandini, M. Bacci, J. Chem. Soc. Chem. Commun. 1985, 731.
5. a) M. D. Vaira, C. A. Ghilardi, S. Midollini, L. Sacconi, J. Am. Chem. Soc. 1978, 100, 2550;
6. b) C. A. Ghilardi, S. Midollini, A. Orlandini, L. Sacconi, Inorg. Chem. 1980, 19, 301.
7. K. Heinze, G. Huttner, L. Zsolnai, P. Schober, Inorg. Chem. 1997, 36, 5457.
8. U. Winterhalter, L. Zsolnai, P. Kircher, K. Heinze, G. Huttner, Eur. J. Inorg. Chem. 2001, 89.
9. 3 group over three positions since the cobalt atom occupies a position at a crystallographic trigonal axis. This appearing disorder problem - which does not affect the accuracy of the determination of the molecular structure to a great extent - might be due to a twin problem or to an overstructure phenomenon. No attempt has been made to untangle this problem.
10. A. Bondi, J. Phys. Chem. 1964, 68, 441.
11. A. Sacco, R. Ugo, J. Chem. Soc. 1964, 3, 3274.
12. S. Beyreuther, J. Hunger, G. Huttner, S. Mann, L. Zsolnai, Chem. Ber. 1996, 129, 745.
13. a) L. Sacconi, S. Midollini, J. Chem. Soc. Dalton Trans. 1972, 1213;
14. b) J. Ellermann, J. Organomet. Chem. 1975, 94, 201;
15. c) J. Ellermann, J. F. Schindler, Chem. Ber. 1976, 109, 1095.
16. 1/n. The solution of the molecular structure in the crystal was straightforward and the agreement factors are satisfactory (see Table 4). A peculiarity is, however, that the ethylene C-C distance was determined as only 116.4(8) pm. Inspection of the size and orientation of the thermal ellipsoids of the ethylene carbon atoms gives a clue to a rational interpretation of this seemingly short C-C distance: the thermal ellipsoids are oriented such that their longest axes almost lie in the C-Co-C plane. This could mean that there are two positions available for the ethylene entity, both of them in the C-Co-C plane, but slightly displaced from the observed position on either side. Further refinement using an appropriate model of disorder, for instance starting with a physically realistic contrained C-C distance, was not considered necessary.
17. S. Beyreuther, J. Hunger, G. Huttner, S. Mann, L. Zsolnai, Chem. Ber. 1996, 129, 745.
18. K. Heinze, G. Huttner, L. Zsolnai, A. Jacobi, P. Schober, Chem. Eur. J. 1997, 3, 732.
19. M. Hesse, H. Meier, B. Zeeh, Spektroskopische Methoden in der organischen Chemie, 4. Auflage, G. Thieme Verlag, Stuttgart, 1991.
20. K. Schwendlick, Organikum, 18th ed., VEB Deutscher Verlag der Wissenschaften, Berlin, 1990.
21. N. E. Schlörer, E. J. Cabrita, S. Berger, Angew. Chem. 2002, 114, 115;
22. Angew. Chem. Int. Ed. 2002, 41, 107.
23. J. H. Gross, N. Nieth, H. B. Linden, U. Blumbach, F. J. Richter, M. E. Tauchert, R. Tompers, P. Hofmann, Anal. Bioanal. Chem. 2006, 386, 52.
24. a) W. Hewertson, H. R. Watson, J. Chem. Soc. 1962, 1490;
25. b) A. Muth, O. Walter, G. Huttner, A. Asam, L. Zsolnai, C. Emmerich, Z. Naturforsch. Teil B 1994, 48, 149.
26. 13C NMR spectra, microanalytical data and IR spectra were of little help.
27. DENZO-SMN, Data processing software, Nonius, 1998; http://www.nonius.com.
28. a) G. M. Sheldrick, SHELXS-97, Program for Crystal Structure Solution, University of Göttingen, 1997; http://shelx.uni-ac. gwdg.de/SHELX/index.html;
29. b) G. M. Sheldrick, SHELXL-97, Program for Crystal Structure Refinement, University of Göttingen, 1997; http://shelx.uni-ac. gwdg.de/SHELX/index.html.
30. International Tables for X-ray Crystallography, vol. 4, Kynoch Press, Birmingham, U. K., 1974.
31. L. Zsolnai, G. Huttner, XPMA, University of Heidelberg, 1994; http://www.uni-heidelberg.de/institute/fak12/AC/huttner/software/ software.html.
32. R. Soltek, Winray 32, University of Heidelberg, 2000; http://www.uni-heidelberg.de/institute/fak12/AC/huttner/software/software.html.