Abstract
The oxidative addition of bromine to homo- and heterobis(carbene) gold(I) complexes 1–6 containing expanded-ring N-heterocyclic carbene (erNHC) ligands was explored to prepare the first examples of gold(III) erNHC complexes. The use of stoichiometric amounts of bromine consistently gave clean gold-centered oxidations leading to the isolation of monocarbene and mixed carbene complexes of the type [AuBr3(erNHC)] (7–9) and trans-[AuBr2(iPr2-bimy)(erNHC)]BF4 (13–15), respectively. The use of excess bromine additionally led to ligand brominations in the monocarbene series affording [AuBr3(erNHCBr2)] complexes (10–12), while in the case of the heterobis(carbene) series, tribromide complexes of the type trans-[AuBr2(iPr2-bimy)(erNHC)]Br3 (16–18) were obtained instead. Comparison of the catalytic activities of all complexes in the hydroamination of alkynes revealed the superior performance of mono-erNHC complexes in all cases.
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