Synthesis of Au^I- and Au^III-Bis(NHC) Complexes: Ligand Influence on Oxidative Addition to Au^I Species

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• 作者：Alba Collado ; Jan Bohnenberger ; Marí ; a-José ; Oliva-Madrid ; Pierrick Nun ; David B. Cordes ; Alexandra M. Z. Slawin and Steven P. Nolan
• 刊名：European Journal of Inorganic Chemistry
• 出版年：2016
• 出版时间：September 2016
• 年：2016
• 卷：2016
• 期：25
• 页码：4111-4122
• 全文大小：2511K
• ISSN：1099-0682c

文摘

The oxidation chemistry of a range of Au^I-bis(NHC) (NHC = N-heterocyclic carbene) complexes with hypervalent iodine(III) oxidants has been explored. Au^I-bis(NHC) precursors have been synthesised by treatment of the corresponding [Au(NHC)Cl] derivatives with imidazol(idin)ium salts in the presence of K₂CO₃. The reactivity of the Au^I complexes towards PhICl₂ has revealed an influence of the nature of the NHC ligands present in the complex on the outcome of the oxidation reaction: small and more strongly electron-donating NHC ligands favoured the formation of a Au^III species. On the basis of these results, a Au^I complex bearing two 1-butyl-3-methylimidazol-2-ylidene (BMIM) ligands has been synthesised. This complex reacted with PhICl₂ and also – for the first time in Au-NHC systems – with PhI(OAc)₂ and PhI(OAc^F)₂ (OAc^F = trifluoroacetate), affording stable Au^III-(NHC)₂ complexes bearing acetate ligands.