Abstract
In elementary chemical bonding theory, a rather neglected concept is a type of chemical bond that Pauling has designated as the “3-electron bond”. This type of bond is usually represented as A···B and it involves three electrons distributed amongst two overlapping atomic orbitals centred on the atoms A and B. Alternative designations are either “3-electron 2-centre” bond or “3-electron 2-orbital” bond.
This is a preview of subscription content, log in via an institution to check access.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
(a) L. Pauling, J. Amer. Chem. Soc., 53, 3225 (1931); (b) L. Pauling, The Nature of the Chemical Bond (Cornell University Press, Ithaca, N.Y., 1960) p. 341.
(a) T. Kiang and R.N. Zare, J. Amer. Chem. Soc., 102, 4024 (1980); (b) A.R. Gregory and V. Malatesta, J. Org. Chem., 45, 122 (1980).
M. Green and J.W. Linnett, J. Chem. Soc., 4959 (1960). See also J.W. Linnett, (a) J. Amer. Chem. Soc., 83, 2643 (1961); (b) The Electronic Structures of Molecules, (Methuen, 1964) p. 55; (c) Sci. Progress (Oxford), 60, 1 (1972). For some pre-1982 discussions of Linnett theory, see (d) R.D. Harcourt and D. Jordan, Specul. Sci. Techn. 3, 77, 612 (1980); (e) R.F. Langler, J.E. Trenholm and J.S. Wasson, Canad. J. Chem., 58, 780 (1980), (f) W.B. Jensen, Canad. J. Chem. 59, 807 (1981).
R.D. Harcourt and G. Winter, J. Inorg. Nucl. Chem., 37, 1039 (1975); 39, 360 (1977).
See for example (a) G.C. Pimentel, J. Chem. Phys., 19, 446 (1951); (b) R.J. Hach and R.E. Rundle, J. Amer. Chem. Soc., 73, 4321 (1951); (c) R.E. Rundle, Records Chem. Progress, 23, 195 (1962); (d) C.A. Coulson, J. Chem. Soc. 1442 (1964).
For some pre-1982 descriptions of systems that can involve 3-centre molecular orbitals for four electrons, see for example (a) N.W. Alcock, Advances in Inorganic and Radiochem., 15, 1 (1972); (b) H.-B. Bürgi, Angewandte Chem. (Int. Ed.) 14, 460 (1975); (c) L. Jansen and R. Block, Angewandte Chem. (Int. Ed.) 16; (d) T.A. Halgren, L.D. Brown, D.A. Kleier and W.N. Lipscomb, J. Amer. Chem. Soc., 99, 6793 (1977); (e) E. Shustorovich, J. Am. Chem. Soc., 100, 7513 (1978); (f) S.S. Shaik, J. Amer. Chem. Soc., 103, 3692 (1981).
L.E. Sutton, Tables of Interatomic Distances, Chemical Society London Special Publications Nos. 11, 18 (1958, 1965).
P.H. Turner and A.P. Cox, J. Chem. Soc. Faraday 2, 74, 533 (1978).
R.H. Jackson, J. Chem. Soc., 4585 (1962).
B.M. Gimarc, Qualitative Molecular Orbital Theory (Benjamin, 1978).
G.N. Lewis, J. Amer. Chem. Soc., 38, 762 (1916); see also Valence and the Structure of Atoms and Molecules (Chemical Catalogue Co., Inc., New York, 1923).
I. Langmuir, J. Amer. Chem. Soc., 41, 868, 1543 (1919).
(a) R.D. Harcourt, Austral, J. Chem., 22, 279 (1969); (b) ibid, and Sillitoe, Austral. J. Chem., 27, 691 (1974); (c) ibid. and A.G. Harcourt, J. Chem. Soc., Faraday II, 70, 743 (1974); (d) ibid. and W. Roso, Canad. J. Chem., 56, 1093 (1978); Int. J. Quantum Chem., 16, 1033 (1979).
L. Pauling, (a) Ref. 2, p. 273; (b) J. Chem. Soc. 1461 (1948).
L. Pauling, Ref. 2, pp. 185, 271.
(a) G.A. Khachkuruzov and I.N. Przhevalskii, Opt. Spectr. (USSR), 46, 586 (1979); (b) D. Cremer and D. Christen, J. Mol. Spectr. 74, 480 (1979).
(a) R.D. Gould and J.W. Linnett, Trans. Faraday Soc., 59, 1001 (1963); (b) J.F. Larcher and J.W. Linnett, J. Chem. Soc. A, 1928 (1967). See also E.F. Hayes and A.K.Q. Siu, J. Amer. Chem. Soc., 93, 2090 (1971).
(a) W.R. Wadt and W.A. Goddard III, J. Amer. Chem. Soc., 97, 3004 (1975); (b) W.A. Goddard III and S.P. Walch, J. Amer. Chem. Soc., 97, 5319 (1975); (c) W.A. Goddard III and B.D. Olafson, Proc. Natl. Acad. Sci. USA, 72, 2335 (1975).
P.C. Hiberty and C. Leforestier, J. Amer. Chem. Soc., 100, 2012 (1978).
R.D. Harcourt, J. Amer. Chem. Soc., 100, 8060 (1978);101, 5456 (1979).
H.A. Bent, Chem. Revs. 68, 587 (1968).
R.D. Harcourt, J. Mol. Struct. (THEOCHEM) (a) 684, 167 (2004). (b) 716, 99 (2005).
R.D. Harcourt, (a) . J. Phys. Chem. A, 101, 2496, 5962 (1997). (b) in Quantum Chemical Methods in Main-Group Chemistry (T.M. Klapötke and A. Schulz, Wiley 1998), pp. 217-250.
R.D. Harcourt, F.L. Skrezenek, R.M. Wilson and R.H. Flegg, J. Chem. Soc. Faraday Trans. 2, 82, 495 (1986).
W. Wu, Yi-R Mo and Q-E Zhang, Chinese J. Chem. 11, 491 (1993).
T.M. Klapötke, J. Li and R.D. Harcourt Inorg. Chim. Acta, 358, 4131 (2005).
A. DeBlase, M. Licata and J.M. Galbraith, J. Phys. Chem. A, 112, 12806 (2008).
B. Braida, C. Walter, B. Engels and P.C. Hiberty, J. Amer. Chem. Soc. 132, 7631 (2010).
Y. Lan, S.E. Wheeler and K.N. Houk, J. Chem. Theory and Comp. 7, 2104 (2011).
R.D. Harcourt, (a) J. Phys. Chem. A, 101, 2496, 5962 (1997). (b) in “Increased-valence Structures in Quantum Chemical Methods in Main-Group Chemistry” (T.M. Klapötke and A. Schulz, Wiley 1998), pp. 217-253. (c) in “Pauling’s Legacy: Modern Modelling of the Chemical Bond”, Theoretical and Computational Chemistry, Vol. 6 (Elsevier Science B.V., Z.B. Maksić and W.J. Orville-Thomas editors, 1999) pp. 449-480.
S. Shaik and P.C. Hiberty, A Chemist’s Guide to Valence Bond Theory, (Wiley-Interscience, New York, 2008), p.249.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
Copyright information
© 2016 Springer International Publishing Switzerland
About this chapter
Cite this chapter
Harcourt, R.D. (2016). Pauling “3-Electron Bonds”, 4-Electron 3-Centre Bonding, and the Need for an “Increased Valence” Theory. In: Bonding in Electron-Rich Molecules. Lecture Notes in Chemistry, vol 90. Springer, Cham. https://doi.org/10.1007/978-3-319-16676-6_2
Download citation
DOI: https://doi.org/10.1007/978-3-319-16676-6_2
Published:
Publisher Name: Springer, Cham
Print ISBN: 978-3-319-16675-9
Online ISBN: 978-3-319-16676-6
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)