RT Journal Article
T1 Stepwise alkyne insertion in Au(I) acetylides: influence of the nuclearity
A1 Cayuela Castillo, Juan
A1 Fernández de Córdova, Francisco J.
A1 See, M. S.
A1 Fernández López, Israel
A1 Ríos, Pablo
AB The reaction between NHC-supported (NHC = N-heterocyclic carbene) gold(I) trimethylsilylacetylide complexes with NHC gold(I) hydroxide species renders different symmetrical homobimetallic Au complexes. These compounds readily undergo migratory insertion of DMAD (dimethyl acetylenedicarboxylate) at 25 °C to give the corresponding bimetallic enyne products. On the contrary, monometallic analogues require much more forcing conditions (excess of DMAD and temperature ≥110 °C) to give the same transformation. Experimental and computational studies reveal that the second metal fragment is responsible for the enhanced nucleophilicity of the reactive carbon atom of the acetylide C[triple bond, length as m-dash]C bond, which initially leads to a more favorable interaction with DMAD in the rate-determining step of an unprecedented, stepwise mechanism where the lability of the Au–C bonds plays an instrumental role. The enhanced reactivity displayed by the bimetallic species was leveraged in the insertion of other substrates such as heterocumulenes.
PB Royal Society of Chemistry
SN 2041-6520
YR 2025
FD 2025-02-13
LK https://hdl.handle.net/20.500.14352/119099
UL https://hdl.handle.net/20.500.14352/119099
LA eng
NO Cayuela-Castillo, J.; Fernández-de-Córdova, F. J.; See, M. S.; Fernández, I.; Ríos, P. Stepwise Alkyne Insertion in Au( i ) Acetylides: Influence of the Nuclearity. Chem. Sci. 2025, 16 (11), 4684–4694. https://doi.org/10.1039/D4SC08227C.
NO This work was supported by the Junta de Andalucía under project ProyExcel_00758. We are also grateful for financial support from grants PID2022-139318NB-I00 and RED2022-134331-T, funded by MICIU/AEI/10.13039/501100011033.
NO Junta de Andalucía
NO Ministerio de Ciencia, Innovación y Universidades (España)
DS Docta Complutense
RD 18 dic 2025