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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. [ABSTRACT FROM AUTHOR]