Insights into the Base‐Stabilized Silylene Nature of the IrSi Bond in Ir(III)–(κ²‐NSi) Complexes with 2‐Quinolone and 2‐Pyridone Type Ligands

A series of Ir–(κ 2 ‐NSi) complexes with 2‐quinolone type ligands have been prepared and characterized to increase our scope of 16e unsaturated Ir–(κ 2 ‐NSi) species to carry out a comprehensive study of the nature of the IrSi bond. Density functional theory calculations with natural bond orbital and quantum theory of atoms in molecules analyses of a range of Ir–silyl(ene) complexes allows the description of the IrSi bond of the examinated complexes as a polarized covalent interaction. The findings of this study also suggest that the most accurate description of this bond in the Ir–(κ 2 ‐NSi) complexes is base‐stabilized silylene. Investigating the silicon environment has been the key for determining the nature of the IrSi bond. This insight also enables to elucidate the base‐stabilized TM–silylene character in other complexes.