Redefining the Mechanistic Scenario of Carbon−Sulfur Nucleophilic Coupling via High‐Valent CpCoIV Species

The potential access to CoIV species for promoting transformations that are particularly challenging at CoIII still remains underexploited in the context of Cp*Co‐catalyzed C−H functionalization reactions. Herein, we disclose a combined experimental and computational strategy for uncovering the participation of Cp*CoIV species in a Cp*Co‐mediated C−S bond‐reductive elimination. These studies support the intermediacy of high‐valent Cp*Co species in C−H functionalization reactions, under oxidative conditions, when involving nucleophilic coupling partners. The joint application of experimental and computational approaches discloses unprecedented mechanistic intricacies associated to Cp*Co‐catalyzed C−H functionalization reactions when using nucleophilic coupling partners. The use of trifluoromethylthiolation reveals an exceptional reductive elimination event from high‐valent Cp*CoIV that can be promoted by either chemical oxidants or electrochemical methods.