Chemical Bonding in Higher Main Group Elements

Abstract Many concepts used for a qualitative description of chemical bonding that originated in the early days of theoretical chemistry have been vindicated recently by quantum chemical calculations, at least as far as first row elements are concerned. However, many concepts that have been justified for first row elements (Li to Ne) cannot—contrary to widespread belief—be generalized to the higher main group elements. This applies particularly to the concept of hybridization, which should be viewed with considerable caution. The essential difference between the atoms of the first and higher rows is that the cores of the former contain only s‐AOs, whereas the cores of the latter include at least s‐ and p‐AOs. As a consequence, the s and p valence AOs of first row atoms are localized in roughly the same region of space, while the p valence AOs of higher row atoms are much more extended in space. This has the consequence that for the light main group elements both lone‐pair repulsion and isovalent hybridization play a greater role than for the heavy main group elements. Furthermore, this implies that single bonds between first row elements are weak and multiple bonds are strong, whereas for the second or higher row elements single bonds are strong and multiple bonds weak. The “extended valence” (violation of the octet rule) observed in compounds of higher main group elements has very little to do with the availability of d‐AOs but is due rather to the size of these atoms and thus to the reduced steric hindrance between ligands and, to a lesser extent, also to the lower electronegativity of the heavy atoms. A model based on the concept of electron‐rich multicenter bonds is certainly closer to reality than one involving hybrids with the participation of d‐AOs. The XO bonds in phosphane oxides, sulfoxides, oxo acids and related compounds are better formulated as semipolar rather than as true double bonds, even if they behave in some respects like double bonds.—The growing interest of theorists in compounds of higher main group elements parallels new and, in some instances, spectacular results of experimental research on the chemistry of these elements.