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(erNHC^Br2)] 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.

中文翻译：

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扩环N-杂环卡宾的金（I）和金（III）配合物：结构，反应性和催化应用。

探索了将溴氧化到含有扩环N-杂环卡宾（erNHC）配体的均双和杂双（卡宾）金（I）配合物1-6中，从而制备了金（III）erNHC配合物的第一个实例。使用化学计量的量的溴的一致，得到干净的金为中心的氧化导致的类型[AuBr的monocarbene和混合碳烯配合物的分离₃（erNHC）]（7-9）和反式- [AuBr ₂（^我镨₂ - bimy）（erNHC）] BF ₄（13-15）。使用过量的溴还会导致单碳烯系列中的配体溴化，从而获得[AuBr ₃（erNHC ^Br2）]配合物（10–12），而在杂双（卡宾）系列的情况下，反式-[AuBr ₂（ⁱ Pr ₂ -bimy）（erNHC）] Br ₃（16–取而代之的是18）。比较所有配合物在炔烃加氢胺化反应中的催化活性，发现在所有情况下mono-erNHC配合物均具有出色的性能。