Opposite Effects of Added AsPh₃ Reveal a Drastic Mechanistic Switch in Rh^I/Au^I Transmetalations via Rh-Au Bonded Intermediates.

ABSTRACT: In contrast with the previously reported decelerating effect of added L (L = AsPh₃) on the Rf/Pf exchange reaction between [Au(Pf)L] and trans-[Rh(Rf)(CO)L₂] (Pf = C₆F₅; Rf = C₆F₃Cl₂-3,5), the Rf/Cl exchange between [AuClL] and trans-[Rh(Rf)(CO)L₂] is accelerated by addition of an excess of L. By combining experimental data and microkinetic modeling, with DFT calculations, the unexpected existence of two cooperative Rf/Cl exchange mechanisms is demonstrated. The opposite kinetic effects of L addition, from negative in the Rf/Pf exchange process, opposing L dissociation in an octahedral rhodium intermediate, to positive in the Rf/Cl exchange, opening an L-catalyzed alternative pathway via t

SUBMITTER: Penas-Defrutos MN 

PROVIDER: S-EPMC12264965 | biostudies-literature | 2025 Jul

REPOSITORIES: biostudies-literature