Yusuke Sunada
Persilylated and related silyl anions have emerged as powerful reagents for the construction of metal-silyl complexes across a wide range of elements. Owing to their strong σ-donating ability and extreme steric bulk, these ligands stabilize highly reactive, low-coordinate metal centers and enable access to unusual bonding motifs and electronic structures. This review summarizes advances in the synthesis, structure, bonding, and reactivity of group 3-10 metal-silyl complexes prepared using persilylated and related silyl anions. Synthetic strategies, particularly salt metathesis with metal halide precursors and related methodologies, are highlighted as versatile routes to both early and late transition metal systems. Recent developments in multidentate and chelating oligosilyl ligands are also emphasized for their role in controlling coordination environments and enabling unique geometries. The reactivity of these complexes, including insertion reactions, σ-bond metathesis, and small-molecule activation, is discussed alongside their catalytic applications in polymerization, hydrosilylation, and hydrogenation. Overall, persilylated silyl ligands provide a versatile platform for advancing organometallic chemistry and catalytic science.