Origin of the different reactivity of the high-valent coinage-metal complexes [RCuⁱⁱⁱ Me₃ ]^- and [RAgⁱⁱⁱ Me₃ ]^- (R=allyl).

ABSTRACT: High-valent tetraalkylcuprates(iii) and -argentates(iii) are key intermediates of copper- and silver-mediated C-C coupling reactions. Here, we investigate the previously reported contrasting reactivity of [RMⁱⁱⁱ Me₃ ]^- complexes (M=Cu, Ag and R=allyl) with energy-dependent collision-induced dissociation experiments, advanced quantum-chemical calculations and kinetic computations. The gas-phase fragmentation experiments confirmed the preferred formation of the [RCuMe]^- anion upon collisional activation of the cuprate(iii) species, consistent with a homo-coupling reaction, whereas the silver analogue primarily yielded [AgMe₂ ]^- , consistent with a cross-coupling reaction. For both complexes, density functional theory calculati

SUBMITTER: Auth T 

PROVIDER: S-EPMC9304237 | biostudies-literature | 2022 Feb

REPOSITORIES: biostudies-literature