A detailed approach into electronic effects of ligands on gold-alkyne interactions has been carried out in the gas phase using tandem mass spectrometry. A semi-empirical method coupled to DFT calculations was used to quantify ligands effects on Au-CC bond strength. To this end, the critical energies of 16 [L-Au-hex-3-yne]+ complexes with different L ligands were determined through collision induced dissociation. It was observed that electron-rich ligands destabilize the gold-alkyne bond, whereas phosphites and carbenes strengthened it. The influence of alkyne electronic effects on the gold-alkyne bond has also been studied by dissociation in tandem mass spectrometry on four different alkynes. In an original approach, two successive ion-molecule reactions within the mass spectrometer were used to measure the relative affinity of gold to an alkyne by exchange reactions. The result is that the more electron-rich the alkyne, the stronger the gold-alkyne bond.

中文翻译：

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从金-炔配合物的键解离能了解金-炔的活化


使用串联质谱法在气相中详细研究了配体对金-炔相互作用的电子效应。使用与 DFT 计算相结合的半经验方法来量化配体对 Au-CC 键强度的影响。为此，通过碰撞诱导解离确定了 16 个具有不同 L 配体的 [L-Au-hex-3-yne]+ 配合物的临界能量。据观察，富电子配体使金-炔键不稳定，而亚磷酸酯和卡宾则增强了金-炔键的稳定性。还通过串联质谱法对四种不同炔烃的解离研究了炔电子效应对金-炔键的影响。在最初的方法中，质谱仪内的两个连续的离子分子反应用于通过交换反应测量金与炔烃的相对亲和力。结果是炔烃的电子越丰富，金-炔键越强。