We reported herein a novel gold(I) bifluoride complex, LAuHF₂, supported by a sterically bulky ligand (L, ^tBuXantphos), that displays exceptional reactivity toward hydrodefluorination (HDF) and hydrosilylation of CO₂ in the presence of hydrosilanes. Compared to the LAuCl counterpart, the LAuHF₂ complex exhibited an over 27-fold increase in turnover frequency in HDF and a 16-times higher turnover number in the hydrosilylation of CO₂. Subsequent experimental and computational studies revealed the counterion effect of non-coordinated fluoride on silane activation, which is critical to synergistically generating an active gold hydride intermediate capable of triggering a sequence of events in the catalytic cycle. This work highlights the prominent counterion effect on gold catalysis and provides new insights into the design of metal catalysts for the synergistic activation of small molecules.

中文翻译：

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氟化物抗衡离子促进金 (I) 催化：加氢脱氟和 CO2 硅氢加成的案例研究

我们在此报道了一种新型二氟化金( I )配合物LAuHF ₂，它由空间大的配体(L, ^t BuXantphos)支撑，在氢硅烷存在下对加氢脱氟(HDF)和CO ₂氢化硅烷化表现出优异的反应活性。与LAuCl对应物相比，LAuHF ₂配合物在 HDF 中的周转频率增加了 27 倍以上，在 CO _{2氢化硅烷化中的周转次数增加了 16 倍}。随后的实验和计算研究揭示了非配位氟化物对硅烷活化的反离子效应，这对于协同生成能够触发催化循环中一系列事件的活性氢化金中间体至关重要。这项工作突出了金催化中显着的抗衡离子效应，并为小分子协同活化的金属催化剂的设计提供了新的见解。