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DOI: 10.1039/A806289G (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 3685-3692

Molecular structure of trimethylamine–gallane, Me3N·GaH3: ab initio calculations, gas-phase electron diffraction and single-crystal X-ray diffraction studies[hair space]†

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Paul T. Brain, Helen E. Brown, Anthony J. Downs, Tim M. Greene, Emma Johnsen, Simon Parsons, David W. H. Rankin, Bruce A. Smart and Christina Y. Tang

Abstract

The structure of the gallane adduct Me3N·GaH3 has been investigated by ab initio quantum chemical calculations. The results of gas-phase electron-diffraction (GED) measurements, together with earlier microwave measurements, have been reanalysed using the SARACEN method to determine the most reliable structure of the gaseous molecule. Salient structural parameters (rαo structure) were found to be: r(Ga–H) 151.1(13), r(Ga–N) 213.4(4), r(N–C) 147.6(3), r(C–H) 108.4(4) pm; H–Ga–N 99.3(8) and Ga–N–C 108.8(2)°. Unlike the corresponding alane derivative, the adduct is monomeric in the crystalline phase with dimensions very close to those of the gaseous molecule, as confirmed by a redetermination of the structure of a single crystal at 150 K.

References

  1. M. J. Taylor and P. J. Brothers, in Chemistry of Aluminium, Gallium, Indium and Thallium, ed. A. J. Downs, Blackie, Glasgow, 1993, pp. 118–128 Search PubMed.
  2. C. R. Pulham, A. J. Downs, M. J. Goode, D. W. H. Rankin and H. E. Robertson, J. Am. Chem. Soc., 1991, 113, 5149 CrossRef CAS.
  3. A. J. Downs and C. R. Pulham, Adv. Inorg. Chem., 1994, 41, 171 CAS.
  4. A. J. Downs and C. R. Pulham, Chem. Soc. Rev., 1994, 23, 175 RSC.
  5. N. N. Greenwood, in New Pathways in Inorganic Chemistry, eds. E. A. V. Ebsworth, A. G. Maddock and A. G. Sharpe, Cambridge University Press, Cambridge, 1968, pp. 37–64 Search PubMed.
  6. C. Jones, G. A. Koutsantonis and C. L. Raston, Polyhedron, 1993, 12, 1829 CrossRef CAS.
  7. C. L. Raston, J. Organomet. Chem., 1994, 475, 15 CrossRef CAS.
  8. B. M. Bulychev, Zh. Neorg. Khim., 1993, 38, 1631 Search PubMed.
  9. See for example, A. A. Melas, US Pat., 4 740 606, 1988(Chem. Abstr., 1988, 109, 121598d) Search PubMed; K. W. Butz, F. M. Elms, C. L. Raston, R. N. Lamb and P. J. Pigram, Inorg. Chem., 1993, 32, 3985 Search PubMed; J. S. Foord, T. J. Whitaker, E. N. Downing, D. O'Hare and A. C. Jones, Appl. Phys. Lett., 1993, 63, 1270 CrossRef CAS; J. S. Foord, A. T. S. Wee, N. K. Singh, T. J. Whitaker and D. O'Hare, Mater. Res. Soc. Symp. Proc., 1993, 282, 27 CrossRef CAS; J. S. Foord, T. J. Whitaker, D. O'Hare and A. C. Jones, J. Cryst. Growth, 1994, 136, 127 CAS; H. Yokoyama and M. Shinohara, Jpn. Kokai Tokkyo Koho, JP 07 226 380, 1995(Chem. Abstr., 1995, 123, 356749g) CrossRef CAS.
  10. J.-W. Hwang, S. A. Hanson, D. Britton, J. F. Evans, K. F. Jensen and W. L. Gladfelter, Chem. Mater., 1990, 2, 342 CrossRef CAS; J.-W. Hwang, J. P. Campbell, J. Kozubowski, S. A. Hanson, J. F. Evans and W. L. Gladfelter, Chem. Mater., 1995, 7, 517 CrossRef CAS.
  11. See, for example, M. J. Henderson, C. H. L. Kennard, C. L. Raston and G. Smith, J. Chem. Soc., Chem. Commun., 1990, 1203 Search PubMed; J. L. Atwood, S. G. Bott, C. Jones and C. L. Raston, Inorg. Chem., 1991, 30, 4868 RSC.
  12. D. O'Hare, J. S. Foord, T. C. M. Page and T. J. Whitaker, J. Chem. Soc., Chem. Commun., 1991, 1445 RSC.
  13. J. L. Atwood, S. G. Bott, F. M. Elms, C. Jones and C. L. Raston, Inorg. Chem., 1991, 30, 3792 CrossRef CAS.
  14. J. L. Atwood, K. D. Robinson, F. R. Bennett, F. M. Elms, G. A. Koutsantonis, C. L. Raston and D. J. Young, Inorg. Chem., 1992, 31, 2673 CrossRef CAS.
  15. F. M. Elms, M. G. Gardiner, G. A. Koutsantonis, C. L. Raston, J. L. Atwood and K. D. Robinson, J. Organomet. Chem., 1993, 449, 45 CrossRef CAS.
  16. F. M. Elms, G. A. Koutsantonis and C. L. Raston, J. Chem. Soc., Chem. Commun., 1995, 1669 RSC.
  17. P. C. Andrews, M. G. Gardiner, C. L. Raston and V.-A. Tolhurst, Inorg. Chim. Acta, 1997, 259, 249 CrossRef CAS.
  18. J. Lorberth, R. Dorn, S. Wocadlo, W. Massa, E. O. Goebel, T. Marschner, H. Protzmann, O. Zseboek and W. Stolz, Adv. Mater. (Weinheim, Fed. Repub. Ger.), 1992, 4, 576 Search PubMed.
  19. P. Jungwirth and R. Zahradník, J. Mol. Struct., THEOCHEM, 1993, 283, 317 CrossRef.
  20. M. Chaillet, A. Dargelos and C. J. Marsden, New J. Chem., 1994, 18, 693 Search PubMed.
  21. K. D. Dobbs, M. Trachtman, C. W. Bock and A. H. Cowley, J. Phys. Chem., 1990, 94, 5210 CrossRef CAS.
  22. K. A. Grencewicz and D. W. Ball, J. Phys. Chem., 1996, 100, 5672 CrossRef CAS.
  23. D. F. Shriver and C. E. Nordman, Inorg. Chem., 1963, 2, 1298 CrossRef CAS.
  24. J. R. Durig, K. K. Chatterjee, Y. S. Li, M. Jalilian, A. J. Zozulin and J. D. Odom, J. Chem. Phys., 1980, 73, 21 CrossRef CAS.
  25. P. L. Baxter, A. J. Downs and D. W. H. Rankin, J. Chem. Soc., Dalton Trans., 1984, 1755 RSC.
  26. 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, 12280 CrossRef CAS.
  27. P. T. Brain, C. A. Morrison, S. Parsons and D. W. H. Rankin, J. Chem. Soc., Dalton Trans., 1996, 4589 RSC.
  28. A. Almenningen, G. Gundersen, T. Haugen and A. Haaland, Acta Chem. Scand., 1972, 26, 3928.
  29. J. L. Atwood, F. R. Bennett, F. M. Elms, C. Jones, C. L. Raston and K. D. Robinson, J. Am. Chem. Soc., 1991, 113, 8183 CrossRef CAS.
  30. GAUSSIAN 94, Revision C.2, M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, 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. P. Stewart, M. Head-Gordon, C. Gonzalez and J. A. Pople, Gaussian Inc., Pittsburgh PA, 1995.
  31. W. J. Hehre, R. Ditchfield and J. A. Pople, J. Chem. Phys., 1972, 56, 2257 CrossRef CAS.
  32. P. C. Hariharan and J. A. Pople, Theor. Chim. Acta, 1973, 28, 213 CrossRef CAS.
  33. M. S. Gordon, Chem. Phys. Lett., 1980, 76, 163 CrossRef CAS.
  34. R. Krishnan, J. S. Binkley, R. Seeger and J. A. Pople, J. Chem. Phys., 1980, 72, 650 CrossRef CAS.
  35. A. D. McLean and G. S. Chandler, J. Chem. Phys., 1980, 72, 5639 CrossRef CAS.
  36. ASYM 40, version 3.0, update of program ASYM 20, L. Hedberg and I. M. Mills, J. Mol. Spectrosc., 1993, 160, 117 Search PubMed.
  37. A. S. F. Boyd, G. S. Laurenson and D. W. H. Rankin, J. Mol. Struct., 1981, 71, 217 CrossRef CAS.
  38. A. W. Ross, M. Fink and R. Hilderbrandt, International Tables for Crystallography, ed. A. J. C. Wilson, Kluwer, Dordrecht, 1992, vol. C, p. 245 Search PubMed.
  39. D. F. Shriver and A. E. Shirk, Inorg. Synth., 1977, 17, 42 CAS.
  40. G. M. Sheldrick, SHELXTL, Version 5, Siemens Analytical X-ray Instruments, Madison, WI, 1995.
  41. C. A. Morrison, B. A. Smart, P. T. Brain, C. R. Pulham, D. W. H. Rankin and A. J. Downs, J. Chem. Soc., Dalton Trans., 1998, 2147 RSC.
  42. A. J. Downs, T. M. Greene, L. A. Harman, P. F. Souter, P. T. Brain, C. R. Pulham, D. W. H. Rankin, H. E. Robertson, M. Hofmann and P. v. R. Schleyer, Inorg. Chem., 1995, 34, 1799 CrossRef CAS.
  43. See, for example, M. Shen and H. F. Schaefer, III, J. Chem. Phys., 1992, 96, 2868 Search PubMed; V. Barone, L. Orlandini and C. Adamo, J. Phys. Chem., 1994, 98, 13185 CrossRef CAS; P. Hunt and P. Schwerdtfeger, Inorg. Chem., 1996, 35, 2085 CrossRef CAS.
  44. See, for example, the discussion and references in B. Ma, J.-H. Lii, K. Chen and N. L. Allinger, J. Am. Chem. Soc., 1997, 119, 2570 Search PubMed.
  45. V. A. Sipachev, J. Mol. Struct. THEOCHEM., 1985, 121, 143 CrossRef; J. Struct. Chem., Engl. Transl., in the press Search PubMed.
  46. B. Beagley and A. R. Medwid, J. Mol. Struct., 1977, 38, 229 CrossRef CAS.
  47. A. Haaland, Angew. Chem., Int. Ed. Engl., 1989, 28, 992 CrossRef.
  48. See, for example, K. R. Leapold in Advances in Molecular Structure Research, eds. M. Hargittai and I. Hargittai, JAI Press, Stamford, 1996, vol. 2 Search PubMed.
  49. C. J. Cramer and W. L. Gladfelter, Inorg. Chem., 1997, 36, 5358 CrossRef CAS.
  50. C. R. Pulham, A. J. Downs, D. W. H. Rankin and H. E. Robertson, J. Chem. Soc., Dalton Trans., 1992, 1509 RSC.
  51. C. R. Pulham, P. T. Brain, A. J. Downs, D. W. H. Rankin and H. E. Robertson, J. Chem. Soc., Chem. Commun., 1990, 177 RSC.
  52. C. R. Pulham, D.Phil. thesis, University of Oxford, 1991.
  53. P. Pullumbi, Y. Bouteiller, L. Manceron and C. Mijoule, Chem. Phys., 1994, 185, 25 CrossRef CAS.
  54. C. M. B. Marsh and H. F. Schaefer, III, J. Phys. Chem., 1995, 99, 195 CrossRef CAS.
  55. P. F. Souter, D.Phil. thesis, University of Oxford, 1995.