RT Journal Article
T1 Haptotropic Phenomena in Digold(I) Triple-Bonded Complexes
A1 Fernández López, Israel
A1 Nieto Vargas, Ignacio
A1 Cayuela Castillo, J.
A1 Fernández de Córdova, Francisco Javier
A1 Ríos, Pablo
AB Addition 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.
PB ACS
YR 2026
FD 2026-04-06
LK https://hdl.handle.net/20.500.14352/134674
UL https://hdl.handle.net/20.500.14352/134674
LA eng
NO Inorg. Chem. 2026, 65, 7153
NO Junta de Andalucía
NO Ministerio de Ciencia, Innovación y Universidades
NO Agencia Estatal de Investigación
DS Docta Complutense
RD 29 abr 2026