18
T.D. Humphries et al. / Journal of Molecular Structure 923 (2009) 13–18
[5] A.J. Arduengo, H.V.R. Dias, J.C. Calabrese, F. Davidson, J. Am. Chem. Soc. 114
(1992) 9724.
[6] J.L. Atwood, K.W. Butz, M.G. Gardiner, C. Jones, G.A. Koutsantonis, C.L. Raston,
K.D. Robinson, Inorg. Chem. 32 (1993) 3482.
[7] F.M. Elms, M.G. Gardiner, G.A. Koutsantonis, C.L. Raston, J.L. Atwood, K.D.
Robinson, J. Organomet. Chem. 449 (1993) 45.
[8] F.R. Bennett, F.M. Elms, M.G. Gardiner, G.A. Koutsantonis, C.L. Raston, N.K.
Roberts, Organometallics 11 (1992) 1457.
[9] O. Stecher, E. Wiberg, Ber. Dtsch. Chem. Ges. 75 (1942) 2003.
[10] E. Wiberg, H. Graf, M. Schmidt, R. Uson, Z. Naturforsch. B 7 (1952) 578.
[11] E. Wiberg, H. Graf, R. Uson, Z. Anorg. Allg. Chem. 272 (1953) 221.
[12] C.J. Harlan, S.G. Bott, A.R. Barron, J. Chem. Crystallogr. 28 (1998) 649.
[13] F.M. Brower, N.E. Matzek, P.F. Reigler, H.W. Rinn, C.B. Roberts, D.L. Schmidt, J.A.
Snover, K. Terada, J. Am. Chem. Soc. 98 (1976) 2450.
and AlH3ꢀNMe3. As would be expected, the corresponding features
are quite similar. The hydride chemical shift for both the 1:1 and
2:1 complexes appears as a very broad singlet, on account of effi-
cient relaxation by the quadrupolar 27Al nucleus. This effect is
more pronounced in the 2:1 complex; with its low symmetry
TBP geometry at the Al nucleus the FWHM of 486 Hz is signifi-
cantly larger than the corresponding value of 63 Hz for the 1:1
counterpart, which displays a pseudo tetrahedral environment at
Al. In a similar vein, the 27Al resonances of the 2:1 and 1:1 adducts
have FWHM values of 1164 and 724 Hz, respectively. The addi-
tional amine ligand in the 2:1 complex causes the hydride 1H
and 27Al resonances to appear at lower frequencies than in the
1:1 species, presumably on account of the increased electron den-
sity at the Al centre. These NMR spectral features are in general
accord with those reported for other amine–alane complexes, such
as AlH3ꢀNMe2Et reported by Frigo et al. [51].
[14] G.K. Lund, J.M. Hanks, H.E. Johnston, Production of
2007.
a-alane, 2007066839,
[15] G.K. Lund, J.M. Hanks, H.E. Johnston, Method for the production of
2005222445, 2005.
a-alane,
[16] I.B. Gorrell, P.B. Hitchcock, J.D. Smith, Chem. Commun. (1993) 189.
[17] C.W. Heitsch, R.W. Parry, C.E. Nordman, Inorg. Chem. 2 (1963) 508.
[18] G.W. Fraser, B.P. Straughan, N.N. Greenwood, J. Chem. Soc. (1963) 3742.
[19] V.S. Mastryukov, A.V. Golubinskii, L.V. Vilkov, J. Struct. Chem. 20 (1979)
788.
4. Conclusions
[20] H.E. Warner, Y. Wang, C. Ward, C.W. Gillies, L. Interrante, J. Phys. Chem. 98
(1994) 12215.
[21] F.M. Elms, C. Jones, C.L. Raston, K.D. Robinson, J. Am. Chem. Soc. 113 (1991)
8183.
[22] P.C. Andrews, M.G. Gardiner, C.L. Raston, V.A. Tolhurst, Inorg. Chim. Acta 259
(1997) 249.
[23] J.K. Ruff, M.F. Hawthorne, J. Am. Chem. Soc. 82 (1960) 2141.
[24] G.W. Schaeffer, E.R. Anderson, J. Am. Chem. Soc. 71 (1949) 2143.
[25] C.W. Heitsch, Nature 195 (1962) 995.
[26] C.M.B. Marsh, H.F. Schaefer, J. Phys. Chem. 99 (1995) 195.
[27] D.B. Beach, S.E. Blum, F.K. Legoues, J. Vac. Sci. Technol. A 7 (1989) 3117.
[28] C. Popov, B. Ivanov, V. Shanov, J. Appl. Phys. 75 (1994) 3687.
[29] T.H. Baum, C.E. Larson, High Temp. Sci. 27 (1989) 237.
[30] H.C. Brown, N.M. Yoon, J. Am. Chem. Soc. 88 (1966) 1464.
[31] SAINT 7.23A, Bruker AXS Inc., Madison, WI, USA, 2006.
[32] G.M. Sheldrick, SADABS, Bruker AXS Inc., Madison, WI, USA, 2004.
[33] G.M. Sheldrick, SHELXS, University of Göttingen, Germany, 2001.
[34] G.M. Sheldrick, SHELXTL 6.14, Bruker AXS Inc., Madison, WI, USA, 2000.
[35] L.J. Farrugia, J. Appl. Crystallogr. 30 (1997) 565.
This study has improved on and extended the structural deter-
mination of AlH3ꢀ2NMe3 published by Heitsch et al. in 1963. We
have confirmed and improved the Cmca room temperature struc-
ture in this earlier study. At ambient temperature, the orientation
of the methyl groups in the Me3N–Al–NMe3 moiety is statistically
disordered. As the temperature of the crystal is decreased, there is
a phase change to Pbcm at around ꢁ55 °C, which we have charac-
terized independently by low-temperature DSC experiments. In
the low temperature Pbcm phase, the orientation of the amine
methyl groups in the Me3N–Al–NMe3 moiety is exclusively mutu-
ally eclipsed, which allows each NMe3 group to adopt a staggered
arrangement with the planar central AlH3 unit. The NMR spectral
characteristics of AlH3ꢀ2NMe3 and its 1:1 counterpart are reported
and are in accord with those of related amine–alane complexes.
[36] A.L. Spek, J. Appl. Crystallogr. 36 (2003) 7.
[37] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman,
J.A. Montgomery, T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar, J.
Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A. Petersson,
H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T.
Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox, H.P. Hratchian,
J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O.
Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. Ayala, K.
Morokuma, G.A. Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S.
Dapprich, A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K.
Raghavachari, J.B. Foresman, J.V. Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J.
Cioslowski, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.L.
Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, M.
Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, C. Gonzalez, J.A.
Pople, Gaussian 03, Revision D.02, Wallingford, CT, 2004.
Acknowledgements
The authors would like to thank Keelie Munroe for assistance
with the DFT calculations presented in Tables 2 and 3, Michael
Johnson for the DSC measurements reported in Fig. 5 and Dr. Larry
Calhoun for NMR spectroscopy assistance. We are grateful to
NSERC and CFI for support of this work, and we thank the Atlantic
Computational Excellence Network (ACEnet) for providing access
to their computing facilities.
[38] A.D. Becke, J. Chem. Phys. 98 (1993) 5648.
[39] C. Lee, W. Yang, R.G. Parr, Phys. Rev. B 37 (1988) 785.
[40] B. Miehlich, A. Savin, H. Stoll, H. Preuss, Chem. Phys. Lett. 157 (1989) 200.
[41] A.D. McLean, G.S. Chandler, J. Chem. Phys. 72 (1980) 5639.
[42] R. Krishnan, J.S. Binkley, R. Seeger, J.A. Pople, J. Chem. Phys. 72 (1980) 650.
[43] R.C. Binning Jr., L.A. Curtiss, J. Comput. Chem. 11 (1990) 1206.
[44] L.A. Curtiss, M.P. McGrath, J.P. Blaudeau, N.E. Davis, R.C. Binning Jr., L. Radorn, J.
Chem. Phys. 103 (1995) 6104.
[45] J.R. Durig, Y.S. Li, J.D. Odom, J. Mol. Struct. 16 (1973) 443.
[46] I. Abderrahim Boutalib, N.-G. Abdellah Jarid, F. Toms, J. Phys. Chem. A 105
(2001) 6526.
Appendix A. Supplementary data
Cartesian coordinates and geometrical parameters at the B3LYP/
6-311G(d,p) level of theory for BH3ꢀNMe3, AlH3ꢀNMe3, AlH3ꢀ2NMe3,
GaH3ꢀNMe3 and GaH3ꢀ2NMe3. Supplementary data associated with
this article can be found, in the online version, at doi:10.1016/
[47] P.T. Brain, H.E. Brown, A.J. Downs, T.M. Greene, E. Johnsen, S. Parsons, D.W.H.
Rankin, B.A. Smart, C.Y. Tang, J. Chem. Soc. Dalton Trans. (1998) 3685.
[48] B. Cordero, V. Gomez, A.E. Platero-Prats, M. Reves, J. Echeverria, E. Cremades, F.
Barragan, S. Alvarez, J. Chem. Soc. Dalton Trans. (2008) 2832.
[49] A. Bondi, J. Phys. Chem. 68 (1964) 441.
[50] T. Steiner, G.R. Desiraju, Chem. Commun. (1998) 891.
[51] D.M. Frigo, G.J.M. Vaneijden, P.J. Reuvers, C.J. Smit, Chem. Mater. 6 (1994) 190.
[52] D.G. Hendrick, C.W. Heitsch, J. Phys. Chem. 71 (1967) 2683.
References
[1] S. Cucinella, A. Mazzel, W. Marconi, Inorg. Chim. Acta 4 (1970) 51.
[2] C. Jones, G.A. Koutsantonis, C.L. Raston, Polyhedron 12 (1993) 1829.
[3] M.G. Gardiner, C.L. Raston, Coord. Chem. Rev. 166 (1997) 1.
[4] M.D. Francis, D.E. Hibbs, M.B. Hursthouse, C. Jones, N.A. Smithies, J. Chem. Soc.
Dalton Trans. (1998) 3249.