doi:10.1002/ejic.202500294engPadilla, MarinaBatuecas, MaríaGarcía-Orduña, PilarOro, Luis A.Fernández-Alvarez, Francisco JoséInsights into the Base-Stabilized Silylene Nature of the Ir--Si Bond in Ir(III)–(κ2-NSi) Complexes with 2-Quinolone and 2-Pyridone Type LigandsART-2025-145845A series of Ir–(κ2‐NSi) complexes with 2‐quinolone type ligands have been prepared and characterized to increase our scope of 16e unsaturated Ir–(κ2‐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–(κ2‐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.2025http://zaguan.unizar.es/record/16381410.1002/ejic.202500294http://zaguan.unizar.es/record/163814oai:zaguan.unizar.es:163814info:eu-repo/grantAgreement/ES/DGA/E42-23Rinfo:eu-repo/grantAgreement/EC/H2020/101034288/EU/International Fellowship Programme for Talent Attraction to the Campus of International Excellence Campus Iberus/IberusExperienceThis project has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement No H2020 101034288-IberusExperienceinfo:eu-repo/grantAgreement/ES/MICINN/PID2021-126212OB-I00European Journal of Inorganic Chemistry 28, 27 (2025), e202500294 [12 pp.]by-nc-ndhttps://creativecommons.org/licenses/by-nc-nd/4.0/deed.esinfo:eu-repo/semantics/openAccess