Direct Evidence for Intermolecular Oxidative Addition of σ(SiSi) Bonds to Gold
作者:Maximilian Joost、Pauline Gualco、Yannick Coppel、Karinne Miqueu、Christos E. Kefalidis、Laurent Maron、Abderrahmane Amgoune、Didier Bourissou
DOI:10.1002/anie.201307613
日期:2014.1.13
Oxidativeaddition plays a major role in transition‐metal catalysis, but this elementary step remains very elusive in gold chemistry. It is now revealed that in the presence of GaCl3, phosphine gold chlorides promote the oxidativeaddition of disilanes at low temperature. The ensuing bis(silyl) gold(III) complexes were characterized by quantitative 31P and 29Si NMR spectroscopy. Their structures (distorted
氧化加成在过渡金属催化中起着重要作用,但是这一基本步骤在金化学中仍然非常难以捉摸。现在揭示出,在GaCl 3的存在下,膦金氯化物在低温下促进乙硅烷的氧化加成。随后的双(甲硅烷基)金(III)配合物通过定量31 P和29 Si NMR光谱进行了表征。它们的结构(扭曲Y形)和σ的反应轮廓(SI Si)的键活化,通过DFT计算分析。这些结果为σ(SiSi)键与金的分子间氧化加成提供了证据,并为开发新的金催化的氧化还原转变开辟了有前途的前景。
FRITZ G.; GRUNERT B., Z. ANORG. UND ALLG. CHEM., 1981, 473, NO 2, 59-79