Evidence for BINAP‐Stabilized Gold(II) Species in a Catalytic Bromination Reaction of Terminal Alkynes

Despite significant advances in gold chemistry, the EPR spectroscopic identification of a transient Au(II) species remains highly challenging. Herein, in the study of a bromination reaction of terminal alkynes enabled by a structurally rigid [Au(BINAP)(TFA)] 2 complex as a precatalyst, a novel BINAP‐stabilized gold(II) intermediate has been generated in situ and identified by EPR spectroscopy in the case of an oxidation reaction of a binuclear [Au(BINAP)(TFA)] 2 with N ‐bromosuccinimide (NBS). Structurally rigid [Au(BINAP)(TFA)] 2 complex is the essential factor to form Au(II) species with triplet spin state and subsequent further dissociation to mononuclear gold species.