Abstract
Three related topics that involve diatomic antibonding orbitals will be discussed in this chapter. First, “increased-valence” structures for 4-electron 3-centre bonding units will be constructed by delocalizing a lone-pair electron on one atom into an antibonding orbital between a pair of adjacent atoms.
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
W.P. Griffiths, Quart. Revs., 16, 188 (1962).
E.W. Abel, Quart. Revs., 17, 133 (1963).
M. Orchin and H.H. Jaffe, “The Importance of Antibonding Orbitals” (Houghton, Mifflin, 1967).
J. Chatt, Pure and Appl. Chem., 24, 425 (1970).
J. Chatt, Proc. Roy. Soc., 172B, 327 (1969).
E.A.C. Lucken, J. Chem. Soc., 2954 (1959).
J.F.A. Williams, (a) Trans. Farad. Soc., 57, 2089 (1961); (b) Tetrahedron, 18, 1477 (1962).
R.D. Spratley and G.C. Pimentel, J. Amer. Chem. Soc., 88, 2394 (1966).
R.G. Pearson, Accounts Chem. Res., 4, 152 (1970).
R.S. Drago and B.D. Corden, Accounts Chem. Res., 13, 353 (1980).
R.D. Harcourt. J. Chem. Educ., 45, 779 (1968) and references 3, 47 and 48 therein; 46, 856 (1969).
R.D. Harcourt, J. Amer. Chem. Soc. (a) 100, 8060 (1978); 101, 5456 (1979); (b) 102, 5195 (1980); 103, 5623 (1981).
K.B. Wiberg, Tetrahedron, 24, 1083 (1968).
R.D. Harcourt, (a) J. Mol. Struct. THEOCHEM 908, 125 (2009). (b) J. Phys. Chem. A, 114, 8573, 8932 (2010).
S. Shaik, D. Danovich, B. Silvi, D. Lauvergnat and P.C. Hiberty, Chem. Eur. J. 11, 6358 (2005).
S. Shaik, D. Danovich, W. Wu and P.C. Hiberty, Nature Chem. 1, 443 (2009).
R.D. Harcourt, (a) J. Phys. Chem. A, 103, 4293 (1999); Addition: 115, 11260 (2003). (b) J. Phys. Chem. A, 114, 8573, 8932 (2010).
R.D. Harcourt, (a) J. Mol. Struct. THEOCHEM, 684, 167 (2004). (b) Aust. J. Chem. 58, 753 (2005). (c) J. Mol. Struct. THEOCHEM, 716, 99 (2005). (d) Aust. J. Chem. 60, 691 (2007).
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). Delocalization of a Lone-Pair Electron into a Vacant Antibonding Orbital: Increased-Valence Structures, Molecular Orbital Theory and Atomic Valencies. In: Bonding in Electron-Rich Molecules. Lecture Notes in Chemistry, vol 90. Springer, Cham. https://doi.org/10.1007/978-3-319-16676-6_14
Download citation
DOI: https://doi.org/10.1007/978-3-319-16676-6_14
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)