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DOI: 10.1039/A707986I (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 545-552

Structures of Ga(hfac)3 and In(hfac)3 (hfac = 1,1,1,5,5,5-hexafluoropentane-2,4-dionate) in the gas phase as studied by electron diffraction and ab initio calculations[hair space]†

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Paul T. Brain, Michael Bühl, Heather E. Robertson, Andrew D. Jackson, Paul D. Lickiss, Donald MacKerracher, David W. H. Rankin, Dipti Shah and Walter Thiel

Abstract

The molecular structures of Ga(hfac)3 and In(hfac)3 (hfac = 1,1,1,5,5,5-hexafluoropentane-2,4-dionate) have been determined by gas-phase electron diffraction (GED) restrained by ab initio computations. The structures, with D3 symmetry, have a distorted octahedral arrangement of oxygen atoms about the central atom such that the E[hair space](hfac) planes are orientated at ca. 82 (E = Ga) and 81° (E = In) to one another. Theoretical computations at the SCF and DFT levels afford structures similar to those found experimentally but with less distorted EO6 octahedra, ca. 89 and 87° (DFT), respectively.

References

  1. R. F. Service, Science, 1996, 272, 1745.
  2. A. Rockett and R. W. Birkmire, J. Appl. Phys., 1991, 70, R81 CrossRef CAS.
  3. P. A. Jones, A. D. Jackson, P. D. Lickiss, R. D. Pilkington and R. D. Tomlinson, Thin Solid Films, 1994, 238, 4 CrossRef CAS.
  4. P. A. Jones, A. D. Jackson, R. D. Pilkington and P. D. Lickiss, Thin Solid Films, 1993, 229, 5 CrossRef CAS.
  5. A. D. Jackson, P. A. Jones, P. D. Lickiss and R. D. Pilkington, J. Mater. Chem., 1993, 3, 429 RSC.
  6. M. J. Hampden-Smith and T. T. Kodas, Chem. Vap. Deposition, 1995, 1, 8 CAS.
  7. The Chemistry of Metal CVD, eds. T. Kodas and M. Hampden-Smith, VCH, Weinheim, 1994 Search PubMed.
  8. P. O'Brien and R. Nomura, J. Mater. Chem., 1995, 5, 1761 RSC.
  9. K. Utsunomiya, Bull. Chem. Soc. Jpn., 1971, 44, 2688 CAS.
  10. H.-K. Shin, K. M. Chi, J. Farkas, M. J. Hampden-Smith, T. T. Kodas and E. N. Duesler, Inorg. Chem., 1992, 31, 424 CrossRef CAS.
  11. C. M. Huntley, G. S. Laurenson and D. W. H. Rankin, J. Chem. Soc., Dalton Trans., 1980, 954 RSC.
  12. S. Cradock, J. Koprowski and D. W. H. Rankin, J. Mol. Struct., 1981, 77, 113 CrossRef CAS.
  13. A. S. F. Boyd, G. S. Laurenson and D. W. H. Rankin, J. Mol. Struct., 1981, 71, 217 CrossRef CAS.
  14. A. W. Ross, M. Fink and R. Hilderbrandt, in International Tables for Crystallography, ed. A. J. C. Wilson, Kluwer, Dordrecht, 1992, vol. C, p. 245 Search PubMed.
  15. W. Hehre, L. Radom, P. v. R. Schleyer and J. A. Pople, Ab initio Molecular Orbital Theory, Wiley, New York, 1986 Search PubMed.
  16. A. Schäfer, C. Huber and R. Ahlrichs, J. Chem. Phys., 1994, 100, 5829 CrossRef.
  17. W. R. Wadt and P. J. Hay, J. Chem. Phys., 1985, 82, 284 CrossRef CAS.
  18. For example, see R. G. Parr and W. Yang, Density Functional Theory of Atoms and Molecules, Academic Press, Oxford, 1989 Search PubMed.
  19. A. D. Becke, Phys. Rev. A, 1988, 38, 3098 CrossRef CAS.
  20. J. P. Perdew, Phys. Rev. B, 1986, 33, 8822 CrossRef; 34, 7406.
  21. O. Treutler and R. Ahlrichs, J. Chem. Phys., 1995, 102, 346 CrossRef CAS.
  22. R. Ahlrichs, M. Bär, M. Häser, H. Horn and C. Kölmel, Chem. Phys. Lett., 1989, 162, 165 CrossRef CAS.
  23. M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheesman, T. A. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. B. Stefanov, A. Nanayakkara, M. Challacombe, C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. J. P. Stewart, M. Head-Gordon, C. Gonzalez and J. A. Pople, GAUSSIAN 94, Gaussian Inc., Pittsburgh, PA, 1995.
  24. R. Ditchfield, Mol. Phys., 1974, 27, 789 CAS; K. Wolinski, J. F. Hinton and P. Pulay, J. Am. Chem. Soc., 1990, 112, 8251 CrossRef CAS.
  25. A. Schäfer, H. Horn and R. Ahlrichs, J. Chem. Phys., 1992, 97, 2571 CrossRef.
  26. M. Häser, R. Ahlrichs, H. P. Baron, P. Weiss and H. Horn, Theor. Chim. Acta, 1992, 83, 455.
  27. M. Bühl, Magn. Reson. Chem., 1996, 34, 782 CrossRef.
  28. A variable-array version of the program ASYM20, L. Hedberg and I. M. Mills, J. Mol. Spectrosc., 1993, 160, 117 Search PubMed; Program adaption from the ASYM40 version undertaken by V. Typke, University of Ulm, Germany CrossRef CAS.
  29. For example, see, G. Rauhut and P. Pulay, J. Phys. Chem., 1995, 99, 3093 Search PubMed and refs. therein.
  30. A. J. Blake, P. T. Brain, H. McNab, J. Miller, C. A. Morrison, S. Parsons, D. W. H. Rankin, H. E. Robertson and B. A. Smart, J. Phys. Chem., 1996, 100, 12 280 CrossRef CAS; P. T. Brain, C. A. Morrison, S. Parsons and D. W. H. Rankin, J. Chem. Soc., Dalton Trans., 1996, 4589 RSC.
  31. For example, see, B. T. Abdo, I. L. Alberts, C. J. Attfield, R. E. Banks, A. J. Blake, P. T. Brain, A. P. Cox, C. R. Pulham, D. W. H. Rankin, H. E. Robertson, V. Murtagh, A. Heppeler and C. Morrison, J. Am. Chem. Soc., 1996, 118, 209 Search PubMed.
  32. Also, see, B. A. Smart, L. E. Griffiths, C. R. Pulham, H. E. Robertson, N. W. Mitzel and D. W. H. Rankin, J. Chem. Soc., Dalton Trans., 1997, 1565 Search PubMed; C. A. Morrison, B. A. Smart, S. Parsons, E. M. Brown, D. W. H. Rankin, H. E. Robertson and J. Miller, J. Chem. Soc., Perkin Trans. 2, 1997, 857 RSC; P. T. Brain, D. W. H. Rankin, H. E. Robertson, M. A. Fox, R. Greatrex, A. Nikrahi and M. Bühl, Inorg. Chem., 1997, 36, 1048 RSC; P. T. Brain, B. A. Smart, H. E. Robertson, M. J. Davis, D. W. H. Rankin, W. J. Henry and I. Gosney, J. Org. Chem., 1997, 62, 2767 CrossRef CAS; N. W. Mitzel, B. A. Smart, S. Parsons, H. E. Robertson and D. W. H. Rankin, J. Chem. Soc., Perkin Trans. 2, 1996, 2727 CrossRef CAS.
  33. B. Ballarin, G. A. Battiston, F. Benetollo, R. Gerbasi, M. Porchia, D. Favretto and P. Traldi, Inorg. Chim. Acta, 1994, 217, 71 CrossRef CAS.
  34. K. Dymock and G. J. Palenik, Acta Crystallogr., Sect. B, 1974, 30, 1364 CrossRef CAS.
  35. B. G. Johnson, P. M. W. Gill and J. A. Pople, J. Chem. Phys., 1993, 98, 5612 CrossRef CAS.
  36. C. W. Murray, G. J. Laming, N. C. Handy and R. D. Amos, Chem. Phys. Lett., 1992, 199, 551 CrossRef CAS.
  37. J. G. Rodriguez, F. H. Cano and S. Garcia-Blanco, Cryst. Struct. Commun., 1979, 8, 53 Search PubMed.
  38. G. J. Palenik and K. R. Dymock, Acta Crystallogr., Sect. B, 1980, 36, 2059 CrossRef.
  39. J. G. Contreras, F. W. B. Einstein and D. G. Tuck, Can. J. Chem., 1974, 52, 3793 CAS.
  40. R. L. Beddoes, D. R. Eardley, F. E. Mabbs, D. Moorcroft and M. A. Passand, Acta Crystallogr., Sect. C, 1993, 49, 1923 CrossRef.
  41. H. Soling, Acta Chem. Scand., Ser. A, 1976, 30, 163.
  42. N. W. Alcock, I. A. Degnan, S. M. Roe and M. G. H. Wallbridge, J. Organomet. Chem., 1991, 414, 285 CrossRef CAS.
  43. J. W. Akitt, in Multinuclear NMR, ed. J. Mason, Plenum Press, New York, 1987, p. 259 Search PubMed.
  44. A. Abragam, The Principles of Nuclear Magnetism, Oxford University Press, Oxford, 1961, p. 314 Search PubMed.
  45. M. Bühl, G. Hopp, W. v. Philipsborn, S. Beck, M.-H. Prosenc, U. Rief and H.-H. Brintzinger, Organometallics., 1996, 15, 778 CrossRef.
  46. J. J. Dechter, U. Henriksson, J. Kowalewski and A.-C. Nilsson, J. Magn. Reson., 1982, 48, 503 CAS.
  47. J. M. Aramini, D. D. McIntyre and H. J. Vogel, J. Am. Chem. Soc., 1994, 116, 11 506 CrossRef CAS.
  48. C. Cerny, J. Machacek, J. Fusek, O. Kriz, B. Casensky and D. G. Tuck, J. Organomet. Chem., 1993, 456, 250 CrossRef CAS.
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