The Chemistry of Hypervalent Molecules

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Abstract
Molecules formed from atoms of Groups V–VIII of the periodic table in their higher valences are studied and a general theory for their electronic and geometric structure is presented. These molecules, which we call hypervalent molecules, are unique in that a donor atom can possess two identical monovalent ligands which are bonded by different types of chemical bonds. The present study provides a simple theoretical description of such molecules using doubly‐occupied lone‐pair orbitals to form hypervalent bonds, and these bonds are divided into two classes as to whether they involve p electrons alone or utilize s electrons as well. While the theoretical classification is of some interest in itself, there are even more interesting problems concerning the physico‐chemical properties of these molecules and the syntheses of new molecules and polymers. We thus present a brief description of the energetics, possibilities for intermolecular inversion and site‐exchange, and synthetic paths for the preparation of hypervalent molecules, as well as indicate a number of new molecules which can probably be synthesized using these ideas.For corrigendum see DOI:10.1002/anie.196901311