Metal complexes containing silicon‐based pincer ligands: Reactivity and application in small molecule activation

Abstract

AbstractThis review highlights the chemical properties of metal complexes supported by silicon‐based tridentate ligands. Silicon donors coordinated to a metal exhibit unique characteristics such as a strong trans influence, σ‐SiH interaction, and metal–ligand cooperativity. Thus, this type of donors ensures distinct reactivity toward various substrates. In particular, the σ‐SiH interaction and mechanism of SiH bond cleavage are discussed. Several attempts to exploit silyl metal complexes for the activation of small molecules, including dinitrogen, carbon dioxide, dihydrogen, and dioxygen, have been reported. This review summarizes recently reported reactions of silyl pincer complexes with small molecules and provides new insights into the possibility of adapting silicon‐based ligands to model the chemistry of biological catalytic systems.