Catalytic Sulfur‐Atom Transfer Enabled by a Bis(disulfide) Titanium Complex

ABSTRACT Multi‐electron processes are key steps in the activation and valorization of small molecules. Due to titanium's electropositivity and the limited accessibility of low‐valent precursors, multi‐electron transformations and their application in atom‐transfer reactions involving this element remain comparatively underdeveloped. Herein, we report a novel four‐electron transformation from a Ti(IV) complex which enabled the formation of a rare titanium bis(disulfide) (Ti(S 2 ) 2 ) in a spiropentane motif. The fast and selective formation of this unique sulfur‐rich complex was leveraged for the catalytic synthesis of isothiocyanates from the corresponding isonitriles. Notably, this reaction is highly efficient even at ambient temperatures and tolerates oxygen‐containing functional groups, marking an advance over noble‐metal catalyzed methods. Detailed mechanistic studies including reaction kinetics and quantum chemical calculations provide insights into the sulfur‐atom transfer process and highlight the role of non‐covalent interactions. Overall, these results represent a new approach in the development of multi‐electron processes and atom‐transfer catalysis with group IV metals.