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Chapter 1

Chemical Bonding of Main‐Group Elements

Martin Kaupp

Technische Universität Berlin, Institut für Chemie, Theoretische Chemie/Quantenchemie, Sekr. C7, Strasse des 17. Juni 115, Berlin 10623, Germany

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First published: 30 May 2014
Cited by: 2

Summary

In this chapter the main principles of main‐group chemical bonding and of important trends in the Periodic Table are reviewed, with the results of modern quantum‐chemical studies in mind. A particular focus is on the radial nodes of atomic orbitals (AOs) and on their consequences for orbital sizes and related chemical properties. The differences between 2p‐elements and their heavier homologues are discussed on the basis of Kutzelnigg's seminal exposition on hybridization defects. Many observations may be explained readily within this framework, including the inert‐pair effect, stereochemically active or inactive lone pairs, nonintuitive relations between bond lengths and binding energies, the stability of N‐heterocyclic carbenes and of related compounds, preferences for multiple bonding, magnetic resonance parameters, and so on. Even the preference for “hypervalency” of the heavier p‐block elements can be related to size and energy of the p‐type valence orbitals of the central atom rather than to extensive d‐orbital participation in bonding. Incomplete screening of nuclear charge by core shells and relativistic effects as important aspects of secondary periodicity are also discussed. Finally, the role of the heavier group 2 atoms as “honorary d‐elements” is scrutinized in the context of unusual structural observations.

Number of times cited: 2

  • , The Nature of the Chemical Bond from a Quantum Mechanical Interference Perspective, ChemistrySelect, 2, 2, (604-619), (2017).
  • , Bonding analysis of ylidone complexes EL2 (E = C–Pb) with phosphine and carbene ligands L, Canadian Journal of Chemistry, 94, 12, (1006), (2016).