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

• Published in: Chemistry, an Asian journal Vol. 13; no. 24; pp. 3800 - 3817
• Main Authors: Guo, Jing‐Dong, Sasamori, Takahiro
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 18.12.2018
• Subjects: Alkynes; Chemical bonds; Chemistry; digermynes; dimetallynes; disilynes; Germanium; group 14 elements; Homology; Lead; main-group elements; Molecular orbitals; Organic chemistry; Quantum chemistry; Reactivity; Silicon; Tin; digermynes; main-group elements; dimetallynes; disilynes; group 14 elements
• ISSN: 1861-4728; 1861-471X
• DOI: 10.1002/asia.201801329

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. 14‐stone heavyweight champion: Recent developments in the area of sterically demanding substituents have facilitated the isolation of stable dimetallynes, that is, compounds that contain a triple bond between heavier group‐14 elements. This review discusses recent reports on the reactivity of such dimetallynes toward small molecules with a focus on those reports that contain a combination of experimental and theoretical (quantum chemical methods) investigations.