Aiming to study the interaction of gold with the highly Lewis acidic fluorenyl cation, we synthesised (-[PhP(CH)Flu)AuCl(tht)][BF] ([2][BF]) and (-PhP(CH)Flu)AuCl (3) (Flu = 9-fluorenyl) and found that the latter could be converted into [(-PhP(CH)Flu)AuCl] ([4]) upon treatment with NaBArF (BArF = B(3,5-CH(CF))). [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.
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