In this work, we report on the synthesis of several organogold(III) complexes based on 4,4’-diterbutylbiphenyl (C^C) and 2,6-bis(4-terbutylphenyl)pyridine (C^N^C) ligands and bond with variously substituted pyridine ligands (pyrR). Altogether 33 com-plexes have been prepared and studied with mass spectrometry using higher-energy collision dissociation (HCD) in an Orbitrap mass spectrometer. A complete methodology including the kinetic modeling of the dissociation process based on the Rice-Ramsperger-Kassel-Marcus (RRKM) statistical method is proposed to obtain critical energies E0 of the pyrR loss for all complexes. The capacity of these E0 values to describe the pyridine ligand effect is further explored, at the same time as more classical descriptors such as 1H pyridinic NMR shift variation upon coordination and Au-NpyrR bond length measured by X-ray diffraction. An extensive theoretical work, including density-functional theory (DFT) and domain-based local pair natural orbital coupled-cluster theory (DLPNO-CCSD(T)) methods, is also carried out to provide bond-dissociation energies which are compared to experimental results. Results show that dissociation energy outperforms others descriptors, in particular to describe ligands effects over a large electronic effects range as seen by confronting the results to the pyrR pKas values. Further insights into the Au-NpyrR bond are obtained through an Energy-Decomposition Analysis (EDA) study which confirms the isolobal character of Au+ with H+. Finally, the correlation between the lability of the pyridine ligands towards the catalytic efficiency of the complexes could be demonstrat-ed in an intramolecular hydroarylation reaction of alkyne. The results were rationalized considering both pre-catalyst activation and catalyst reactivity. This study establishes the possibility of correlating dissociation energy, which is a gas-phase descriptor, with condensed-phase parameters such as catalysis efficiency. It holds therefore great potential for inorganic and organometallic chem-istry by opening a convenient and easy way to evaluate the electronic influence of a ligand towards a metallic center.