Synthesis of Titanium ĸ¹<i>S</i>‐Thioamidato Complexes from Reactions of Bis(pentafulvene)complexes with Isothiocyanates

As part of the activation of small molecules by transition metal complexes, reactions of bis(π‐η 5 :σ‐η 1 ‐pentafulvene)titanium complexes with various isothiocyanates are performed. Despite the presence of two double bonds, only the CS bond reacts in this competing reaction, resulting in the selective formation of titanium ĸ 1 S thioamidato complexes. The insertion reaction occurs under mild conditions by the attack of the nucleophilic TiC exo atom of the pentafulvene moiety on the central carbon atom of the isothiocyanate. Besides the reaction with an additional equivalent of isothiocyanate to form bis‐ĸ 1 S thioamidato complexes, the reaction with H‐acidic and multiple‐bond‐containing substrates leads to further functionalized complexes. The selective formation of the ĸ 1 S binding mode compared to a possible ĸ 1 N binding mode is further supported by DFT calculations, while the structures are confirmed by NMR spectroscopy and single‐crystal X‐ray diffraction.