Hyperbonding and Hypercoordination in Main-Group Chemistry

The aim of the chapter is to survey the strong attractive intramolecular X ← Y interactions of 1,5-type occurring between terminal main-group 14–16 centers (X) and electron-rich atoms Y (Y = O, S, NR, and others) in various compounds resulting in significant stabilization of cis-s-cis structure of these molecules. Theoretical approaches to stabilization and design of nonclassical compounds containing p elements of the second period (B, C, N, O, F) in the nonmetal network environments are considered. Structural diversity of such type systems is demonstrated, and the influence of steric and electronic factors on their stability is considered.