Scope and Limitations of TBA[Fe]‐Catalyzed Carbene Transfer to X−H‐bonds – Indication of a Mechanistic Dichotomy

Abstract

Abstract An in‐depth study of carbene transfer reactions into polar X−H‐bonds catalyzed by the nucleophilic Fe‐complex Bu 4 N[Fe(CO) 3 (NO)] (TBA[Fe]) is presented. Whereas alcohols are unreactive, thiols and secondary amines are reactive, silanes showed modest activities. Hammett correlations indicate the presence of an X−H‐acidity dependent mechanistic dichotomy.