EaStCHEM School of Chemistry, University of St Andrews, North Haugh, St Andrews, KY16 9ST UK.
Chemistry. 2011 Jan 24;17(4):1238-46. doi: 10.1002/chem.201002607. Epub 2010 Dec 16.
The synthesis of a series of dinuclear gold hydroxide complexes has been achieved. These complexes of type [{Au(IPr)}(2)(μ-OH)]X (X=BF(4), NTf(2), OTf, FABA, SbF(6); IPr=2,6-bis(disopropylphenyl)imidazol-2-ylidene; NTf(2)=bis(trifluoromethanesulfonyl)imidate; OTf=trifluoromethanesulfonate; FABA=tetrakis(pentafluorophenyl)borate) are easily formed in the presence of water and prove highly efficient in the catalytic hydration of nitriles. Their facile formation in aqueous media suggests they are of relevance in gold-catalyzed reactions involving water. Additionally, a series of [Au(IPr)(NCR)][BF(4)] (R=alkyl, aryl) complexes was synthesized as they possibly occur as intermediates in the catalytic reaction mechanism. (1)H and (13)C NMR data as well as key bond lengths obtained by X-ray diffraction studies are compared and reveal an interesting structure-activity relationship. The collected data indicate a negligible effect of the nature of the nitrile on the reactivity of [Au(L)(NCR)][X] complexes in catalysis.
已经合成了一系列双核金氢氧化物配合物。这些[{Au(IPr)}(2)(μ-OH)]X（X=BF(4), NTf(2), OTf, FABA, SbF(6)；IPr=2,6-双（二异丙基苯基）咪唑-2-亚基；NTf(2)=双（三氟甲磺酰基）亚胺；OTf=三氟甲磺酸根；FABA=四（五氟苯基）硼酸盐）类型的配合物很容易在水的存在下形成，并在腈的催化水合中证明非常有效。它们在水介质中的易形成表明它们与涉及水的金催化反应有关。此外，还合成了一系列[Au(IPr)(NCR)][BF(4)]（R=烷基，芳基）配合物，因为它们可能是催化反应机理中的中间产物。（1）H 和（13）C NMR 数据以及通过 X 射线衍射研究获得的关键键长进行了比较，揭示了有趣的结构-活性关系。收集的数据表明，腈的性质对[Au(L)(NCR)][X]配合物在催化中的反应性影响可以忽略不计。
