Methyl–hydride metathesis between [Zr(cp)2Me2] and [HAl(µ3-NBut)]4: molecular structures of [Me1-xHxAl(µ 3-NBut)]4 (x = 0, 0.78 or 1) and [(cp)2ZrMe(µ-H)]2 (cp = η5-C5H5) [hair space]

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C. Jeff Harlan, Simon G. Bott and Andrew R. Barron


Abstract

The reaction of [Zr(cp)2Me2] (cp = η5-C5H5) with the cubane iminoalane, [HAl(µ3-NBut)]4, yielded [(cp)2ZrMe(µ-H)]2 and the alkyl-substituted iminoalanes [Al4MeH33-NBut)4 ] 1 and [Al4Me2H23-NBut )4] 2. The dimer [(cp)2ZrMe(µ-H)]2 decomposes above 60 °C. The methyl–hydride exchange is first order with respect to each reactant concentration, and ΔH[hair space] and ΔS[hair space] have been determined as 104(1) kJ mol-1 and 18.8(4) J K-1 mol-1, respectively. The molecular structures of [(cp)2ZrMe(µ-H)]2, [HAl(µ3-NBut)]4, [MeAl(µ3-NBut)]4 and a cocrystallization disorder of compounds 1, 2 and [HAl(µ3-NBut)]4 have been determined by X-ray crystallography.


References

  1. M. Bochmann, J. Chem. Soc., Dalton Trans., 1996, 255 RSC  and refs. therein.
  2. A. R. Barron, Organometallics, 1995, 14, 3581 CrossRef CAS .
  3. C. J. Harlan, S. G. Bott and A. R. Barron, J. Am. Chem. Soc., 1995, 117, 6465 CrossRef CAS .
  4. M. R. Mason, J. M. Smith, S. G. Bott and A. R. Barron, J. Am. Chem. Soc., 1993, 115, 4971 CrossRef .
  5. C. J. Harlan, M. R. Mason and A. R. Barron, Organometallics, 1994, 13, 2957 CrossRef CAS .
  6. Y. Koide, S. G. Bott and A. R. Barron, Organometallics, 1996, 15, 2213 CrossRef CAS .
  7. R. W. Lenz, J. Yang, B. Wu, C. J. Harlan and A. R. Barron, Can. J. Microbiol., 1995, 41, 274 CAS .
  8. B. Wu, C. J. Harlan, R. W. Lenz and A. R. Barron, Macromolecules, in the press .
  9. Y. Koide, S. G. Bott and A. R. Barron, Organometallics, 1996, 15, 2213 CrossRef CAS .
  10. M. B. Power, J. W. Ziller and A. R. Barron, Organometallics, 1992, 11, 1055 CrossRef CAS ; S. Schulz, H. W. Roesky, H. J. Koch, G. M. Sheldrick, D. Stalke and A. Kuhn, Angew. Chem., Int. Ed. Engl., 1993, 32, 1729 CrossRef ; W. Uhl, R. Graupner, M. Layh and U. Schütz, J. Organomet. Chem., 1995, 93, C1 CrossRef CAS .
  11. C. J. Harlan and A. R. Barron, J. Cluster Chem., 1996, 7, 455 Search PubMed .
  12. See, for example, S. Amirkhalili, P. B. Hitchcock and J. D. Smith, J. Chem. Soc., Dalton Trans., 1979, 1206 Search PubMed ; P. B. Hitchcock, J. D. Smith and K. M. Thomas, J. Chem. Soc., Dalton Trans., 1976, 1433 RSC ; K. Gosling, J. D. Smith and D. H. W. Wharmby, J. Chem. Soc. A, 1969, 1738 RSC .
  13. See, for example, G. Del Piero, M. Cesari, G. Perego, S. Cucinella and E. Cernia, J. Organomet. Chem., 1977, 129, 289 Search PubMed ; M. Cesari, G. Perego, G. Del Piero, S. Cucinella and E. Cernia, J. Organomet. Chem., 1974, 78, 203 CrossRef CAS .
  14. P. C. Wailes and H. Weigold, J. Organomet. Chem., 1970, 24, 405 CrossRef CAS .
  15. R. F. Jordon, C. S. Bajgur, W. E. Dasher and A. L. Rheingold, Organometallics, 1987, 6, 1041 CrossRef .
  16. K. I. Gell and J. Schwartz, J. Am. Chem. Soc., 1978, 100, 3246 CrossRef CAS ; J. M. Manriquez, D. R. McAlister, R. D. Sanner and J. E. Bercaw, J. Am. Chem. Soc., 1978, 100, 2716 CrossRef CAS ; F. D. Miller and R. D. Sanner, Organometallics, 1988, 7, 818 CrossRef CAS .
  17. H. Alt and M. D. Rausch, J. Am. Chem. Soc., 1974, 96, 5936 CrossRef CAS ; D. R. McAlister, D. K. Erwin and J. E. Bercaw, J. Am. Chem. Soc., 1978, 100, 5966 CrossRef CAS .
  18. G. Del Piero, G. Perego, S. Cucinella, M. Cesari and A. Mazzei, J. Organomet. Chem., 1977, 136, 13 CrossRef CAS .
  19. C. H. Langford and H. B. Gray, Ligand Substitution Processes, W. A. Benjamin, New York, 1965 Search PubMed .
  20. J. J. Eisch, in Comprehensive Organometallic Chemistry, eds. G. Wilkinson, F. G. A. Stone and E. W. Abel, Pergamon, Oxford, 1982, vol. 1, ch. 6 Search PubMed ; Coordination Chemistry of Aluminum, ed. G. H. Robinson, VCH, New York, 1993 Search PubMed .
  21. G. Del Piero, M. Cesari, G. Dozzi and A. Mazzei, J. Organomet. Chem., 1977, 129, 281 CrossRef CAS ; T. R. R. McDonald and W. S. McDonald, Acta Crystallogr., Sect. B, 1972, 28, 1619 CrossRef CAS .
  22. A. R. Barron and G. Wilkinson, Polyhedron, 1986, 5, 1897 CrossRef CAS ; B. M. Bulychev, Polyhedron, 1990, 9, 387 CrossRef CAS .
  23. G. Del Piero, G. Perego, S. Cucinella and M. Cesari, J. Organomet. Chem., 1977, 136, 13 CrossRef CAS .
  24. M. B. Power, A. R. Barron, D. Hnyk, G. McMurdo and D. W. H. Rankin, Adv. Mater. Optics Electron., 1995, 5, 177 CrossRef CAS ; C. J. Harlan, E. G. Gillan, S. G. Bott and A. R. Barron, Organometallics, in the press .
  25. S. B. Jones and J. L. Peterson, Inorg. Chem., 1981, 20, 2889 CrossRef CAS .
  26. K. Prout, T. S. Cameron, R. A. Forder, S. R. Critchley, B. Denton and G. V. Rees, Acta Crystallogr., Sect. B, 1974, 30, 2290 CrossRef ; J. L. Atwood, R. D. Rogers, W. E. Hunter, C. Floriani, G. Fechinetti and A. Chiesi-Villa, Inorg. Chem., 1980, 19, 3812 CrossRef CAS .
  27. E. Samuel and M. D. Rausch, J. Am. Chem. Soc., 1973, 95, 6263 CrossRef CAS .
  28. S. Cucinella, T. Salvatori, C. Busetto, G. Perego and A. Mazzei, J. Organomet. Chem., 1974, 78, 185 CrossRef CAS ; S. Cucinella, G. Dozzi, A. Mazzei and T. Salvatori, J. Organomet. Chem., 1975, 90, 257 CrossRef CAS .
  29. M. C. Burla, M. Camalli, G. Cascarano, C. Giacovazzo, G. Polidori, R. Spagna and D. Viterbo, J. Appl. Crystallogr., 1989, 22, 389 CrossRef CAS .
  30. MOLEN, An Interactive Structure Solution Procedure, Enraf-Nonius, Delft, 1990 .
  31. G. M. Sheldrick, SHELXL 93; University of Göttingen, 1993 .
  32. International Tables for X-Ray Crystallography, Kynoch Press, Birmingham, 1974, vol. 4 Search PubMed .
  33. M. D. Healy, D. A. Wierda and A. R. Barron, Organometallics, 1988, 7, 2543 CrossRef CAS .
  34. Nicolet Instruments Corporation, Madison, WI, 1988 .
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