Fernández López, IsraelNieto Vargas, IgnacioCayuela Castillo, J.Fernández de Córdova, Francisco JavierRíos, Pablo2026-04-132026-04-132026-04-06Inorg. Chem. 2026, 65, 715310.1021/acs.inorgchem.5c04642https://hdl.handle.net/20.500.14352/134674Addition of either IPrAuOTf or IPrCuOTf (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; OTf = trifluoromethanesulfonate anion) to the digold acetylide IPrAuC≡CAuIPr results in the selective formation of the corresponding trimetallic cationic species [IPrAuC≡C(π-MIPr)AuIPr][OTf] (M = Au or Cu). Variable-temperature 1H NMR experiments (VT-NMR) reveal that while the homotrimetallic gold complex exhibits dynamic σ,π-exchange in solution at temperatures even as low as −130 °C, the heterometallic analogue presents a static scenario. On the other hand, extension of the acetylide bridge by one additional acetylide unit using IPrAuC≡C–C≡CAuIPr introduces a new fluxional process in the corresponding analogous trimetallic compounds [IPrAuC≡C(π-MIPr)–C≡CAuIPr][OTf] (M = Au or Cu), namely π,π-exchange. In the case of the copper-containing complex, this exchange occurs even at low temperatures, whereas exchange can be thermally arrested in the trigold system at temperatures below −10 °C. Computational studies indicate that the divergent behavior between gold and copper regarding π,π-exchange does not appear to stem from their interaction with the alkyne fragment but rather in how this interaction changes along the reaction coordinate toward the transition state geometry.engAttribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/journal articlehttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5c04642open access546Química inorgánica (Química)2303 Química Inorgánica