A cationic gold-fluorenyl complex with a dative Au → C+ bond: synthesis, structure, and carbophilic reactivity

Abstract

Aiming to study the interaction of gold with the highly Lewis acidic fluorenyl cation, we synthesised (o-[Ph₂P(C₆H₄)Flu)AuCl(tht)][BF₄] ([2][BF₄]) and (o-Ph₂P(C₆H₄)Flu)AuCl₂ (3) (Flu = 9-fluorenyl) and found that the latter could be converted into [(o-Ph₂P(C₆H₄)Flu)AuCl]⁺ ([4]⁺) upon treatment with NaBArF₂₄ (BArF₂₄ = B(3,5-C₆H₃(CF₃)₂)₄). [4]⁺, which has been isolated as a chloride-bridged dimer, readily catalyses the cycloisomerisation of 2-allyl-2-(2-propynyl)malonate. Computational results show that [4]⁺ possesses a strong Au → C⁺ bond and readily activates enynes.