Synthesis and Characterization of Gold(III) Complexes Bearing a Picoline‐functionalized N‐Heterocyclic Carbene

3‐Methyl‐1‐(2‐picolyl)‐imidazolium chloride ( 1 ) has been synthesized and used as a precursor for the preparation of the (NHC)AgCl complex [NHC = 3‐methyl‐1‐(2‐picolyl)imidazol‐2‐ylidene] ( 2 ). Transmetalation of 2 with (tht)AuBr (tht = tetrahydrothiophene) yields the corresponding (NHC)AuBr complex 3 , which is further oxidized by Br 2 to give the (NHC)AuBr 3 compound 4 . Treatment of 4 with one equivalent of solid AgBF 4 affords the [(NHC)AuBr 2 ][BF 4 ] congener 5 as a pale green, crystalline powder. The structure of 4 and 5 were determined by single‐crystal X‐ray diffraction, revealing for 5 a κ‐N‐coordination of the Au III atom by the picolyl nitrogen atom. Further attempts to exchange all bromides by carboxylates results in the reduction to the dimeric Au I compound [(NHC) 2 Au 2 ][BF 4 ] 2 , 6 .