Activation of Small Molecules by Compounds that Contain Triple Bonds Between Heavier Group‐14 Elements

Abstract

Dimetallynes (RE≡ER; E=Si, Ge, Sn, Pb), i.e., systems that contain triple bonds between heavier group‐14 elements represent the heavier homologues of alkynes. The high reactivity of disilynes, digermynes, distannynes, and diplumbynes can be interpreted in terms of their unique bonding situation, which includes a trans‐bent structure, a small HOMO–LUMO gap, a partial diradical character, their electronic nature, and interactions between bulky substituents. Relatively recent developments in the area of sterically demanding substituents have permitted isolating some stable compounds with a triple bond between heavier group‐14 elements. The structural features of these triple‐bonded compounds and their reactivity toward small molecules have been investigated using experimental and theoretical approaches. This review focuses on recent developments regarding the reactivity of stable compounds with a triple bond between heavier group‐14 elements toward small molecules, where the results were examined using quantum chemical methods. A comprehensive review on carbon chemistry is beyond the scope of this focus review.