RT info:eu-repo/semantics/article
T1 Intimate relationship between C–I reductive elimination, aryl scrambling and isomerization processes in Au(iii) complexes
A1 Fernández Moyano, Sara
A1 Marcos Ayuso, Guillermo
A1 Peñas de Frutos, Marconi Nicolás
A1 Espinet Rubio, Pablo
K1 Isomerización en complejos
K1 Isomerization processes
K1 23 Química
AB 19F NMR monitoring shows that heating trans-[AuIIIRf2I2]− solutions (Rf = C6F3Cl2-3,5) leads to formation of cis-[AuRf2I2]−, [AuRf3I]− and [AuRfI3]−via kinetic competition between isomerization and Rf/I scrambling. The system evolution is driven by the easy Rf–I reductive elimination from [AuRfI3]− (forming also [AuI2]−), which is faster than any of the Rf–Rf couplings from the coexisting species, hindering the commonly desired and thermodynamically preferred C–C coupling. A kinetic model where I− dissociation triggers both isomerization and transmetalation steps is proposed, which fits well the experimental data. DFT calculations support that the lower bond strength of AuIII–I compared to other halides produces a pathway switch that makes C–I coupling kinetically preferred. Consequently, it is better avoided in reactions looking for C–C coupling.
PB Royal Society of Chemistry
SN 1359-7345
YR 2023
FD 2023
LK https://uvadoc.uva.es/handle/10324/59445
UL https://uvadoc.uva.es/handle/10324/59445
LA eng
NO Chemical Communications, 2023, 59, 1975-1978
NO Producción Científica
DS UVaDOC
RD 17-jul-2024