Gentleman Alexander S, Green Alice E, Price Daniel R, Cunningham Ethan M, Iskra Andreas, Mackenzie Stuart R
Physical and Theoretical Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford, OX1 3QZ UK.
Top Catal. 2018;61(1):81-91. doi: 10.1007/s11244-017-0868-z. Epub 2017 Oct 30.
A combined spectroscopic and computational study of gas-phase Au(CH) ( = 3-8) complexes reveals a strongly-bound linear Au(CH) core structure to which up to four additional ligands bind in a secondary coordination shell. Infrared resonance-enhanced photodissociation spectroscopy in the region of the CH and fundamental transitions reveals essentially free internal rotation of the core ligands about the HC-Au-CH axis, with sharp spectral features assigned by comparison with spectral simulations based on density functional theory. In separate experiments, vibrationally-enhanced dehydrogenation is observed when the vibrational normal mode in methane is excited prior to complexation. Clear infrared-induced enhancement is observed in the mass spectrum for peaks corresponding 4u below the mass of the Au(CH) complexes corresponding, presumably, to the loss of two H molecules.
对气相Au(CH) （n = 3 - 8）配合物进行的光谱与计算联合研究表明，存在一个强束缚的线性Au(CH)核心结构，在二级配位层中最多有四个额外配体与之结合。在CH 和 基频跃迁区域的红外共振增强光解离光谱显示，核心配体围绕HC - Au - CH轴基本可以自由内旋转，通过与基于密度泛函理论的光谱模拟进行比较，确定了尖锐的光谱特征。在单独的实验中，当在络合之前激发甲烷中的 振动简正模式时，观察到了振动增强的脱氢反应。在质谱中，对于质量比Au(CH) 配合物质量低4u的峰，观察到明显的红外诱导增强，这可能对应于两个H分子的损失。
