Abstract
The octet rule fails to predict the stoichiometrics of binary lithium compounds of first row elements. There is now gas phase experimental evidence for OLi3, OLi4, OLi5, and OLi5; many similar perlithiated species are predicted computationally to be highly stable thermodynamically towards all possible dissociation modes. The structures of NLi4, OLi4, and FLi4, for example, are tetrahedral while CLi5, NLi5, and OLi5 favor trigonal bipyramidal (D3h) symmetries. CLi6, and CLi6 are octahedral. The extra (ninth and tenth) valence electrons occupy totally symmetric (a1) molecular orbitals, largely lithium-lithium bonding in character. A simple interpretation assigns only an octet of electrons to the central atom, and any additional electrons to the surrounding lithium cage.
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References
Kos, A.J.; Jemmis, E.D.; Schleyer, P.v.R.; Gleiter, R.; Fischbach, U.; Pople, J.A.: 1981, J. Am. Chem. Soc. 103, p.4996; Apeloig, Y.; Clark, T.; Kos, A.J.; Jemmis, E.D.; Schleyer, P.v.R.: 1980, Israel J. Chem. 20, p. 43. This paper lists earlier references.
Lewis, G.N.: 1916, J. Am. Chem. Soc. 38, p. 762; Kossel, W.: 1916, Ann. Phys. 49, p. 229.
Gaussian 76: Binkley, J.S.; Whiteside, R.; Hariharan, P.C.; Seeger, R.; Pople, J.A.; Hehre, W.J.; Newton, M.D.: 1979, QCPE 11, 368; Gaussian 80: Binkley, J.S.; Whiteside, R.; Krishnan, R.; Seeger, R.; DeFrees, D.J.; Schlegel, H.B.; Topiol, S.; Kahn, L.R.; Pople, J.A.: 1981, QCPE 10, 416.
Pople, J.A.; Binkley, J.S.; Seeger, R.: 1976, Int. J. Quant. Chem. Symp. 10, p. 1. For the 3-21G basis set, see Binkley, J.S.; Pople, J.A.; Hehre, W.J.: 1980, J. Am. Chem. Soc. 102, p. 939. For absolute energies and fuller descriptions of most of the species in the present paper, see the “Carnegie-Mellon Quantum Chemistry Archive”, Whiteside, R.A.; Frisch, M.J.; Binkley, J.S.; DeFrees, D.J.; Schlegel, H.B.; Raghavachari, K.; Pople, J.A.: 1981, 2nd Ed., Carnegie-Mellon University.
Pauling, L.A.: 1937, J. Am. Chem. Soc. 53, p. 1367.
Clark, T.: 1981, J.C.S. Chem. Comm. p. 515 and unpublished calculat¬ions;
Peyerimhoff, S.D., Buenker, R.J.: 1979, Chem. Phys. Lett. 65, p. 434;
Candell, E.; Karafiloglou, P.; Salem, L.; 1980, J. Am. Chem. Soc. 102, p. 855. For recent experimental references, see:
Wang, J.T.; Williams, F.: 1980, J. Am. Chem. Soc. 102, p. 2860;
Hasegawa, A.; Hudson, R.L.; Kikuchi, O.; Nishikida, K.; Williams, F.: 1981, ibid. 103, p. 3436.
Allen, L.C.: private communication. WUrthwein, E.-U.: unpublished calculations calculations.
Olah, G.A.; Donovan,D.J.; Shen, J.; Klopman, G.: 1975, J. Am. Chem. Soc. 97, p. 3559.
Brown, H.C. (with comments by Schleyer, P.v.R., “The Nonclassical Ion Problem”, 1977, Plenum Press, New York, pp. 13–19.
For leading references, see Wolfe, S.; Mitchell, D.J.; Schlegel, H.B.: 1981, J. Am. Chem. Soc. 103, p. 7692 and p. 7694.
Nicely, V.A.; Dye, J.L.: 1970, J. Chem. Phys. 52, p. 4795.
Trenary, M.; Schaefer III, H.F.; Kollman, P.: 1977, J. Am. Chem. Soc. 99, p. 3885; 1978, J. Chem. Phys. 70, p. 1815.
Wu, C.H.; Kudo,H.; Ihle, H.R.: 1979, J. Chem. Phys. 70, p. 1815.
For references, see Gurak, J.A.; Chinn, Jr., J.W.; Lagow, R.J.; 1982, J. Am. Chem. Soc. 104, p. 2637. For CLi5,
Jemmis, E.D.; Chandrasekhar, J.; Wurthwein, E.-U.; Scnleyer, P.v.R.; Chinn, Jr., J.W.; Landro, F.J.; Luke, B.; Pople, J.A.: 1982, ibid. 104, in press.
Wu, C.H., private communication. See Wu, C.H.; Ihle, H.R.: 1979, Chem. Phys. Lett. 61, p. 54
Chandrasekhar, J.; Pople, J.A.; Seeger, R.; Seeger, U.; Schleyer, P.v.R.: 1982, J. Am. Chem. Soc. 105, in press.
Peterson, K.I.; Dao, P.D.; Castleman, Jr., A.W.: 1982, 183rd Am. Chem. Soc. National Meeting, Las Vegas, Nevada, Abstract PHYS 173.
Simon, A.: 1979, Structure and Bonding 36, p. 81.
Kollman, P.; Liebman, J.F.; Allen, L.C.: 1970, J. Am. Chem. Soc. 92, p. 1142. For an earlier study of Li2F,
Pearson, P.K.; Hunt, W.J.; Bender, C.F.; Schaefer III, H.F.: 1973, J. Chem. Phys. 58, p. 5383.
Collins, J.B.; Schleyer, P.v.R.; Binkley, J.S.; Pople, J.A.; Radom, L.: 1976, J. Am. Chem. Soc. 98, p. 3436.
Siegbahn, P.E.M.: 1982, Chem. Phys. 66, p. 443;
Pople, J.A.; Tidor, B.; Schleyer, P.v.R.: 1982, Chem. Phys. Lett., in press.
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von Ragué Schleyer, P. (1983). Are CLi6, NLi5, OLi4, Etc, Hypervalent?. In: Löwdin, PO., Pullman, B. (eds) New Horizons of Quantum Chemistry. International Academy of Quantum Molecular Science, vol 4. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-7950-5_9
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DOI: https://doi.org/10.1007/978-94-009-7950-5_9
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