Journal article

Origin of the different reactivity of the high-valent coinage-metal complexes [RCuIIIMe3]- and [RAgIIIMe3]- (R = allyl).

Thomas Auth, Christopher J Stein, Richard AJ O'Hair, Konrad Koszinowski

Chemistry | Published : 2021

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 [RM III Me 3 ] - 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 [AgMe 2 ] - , consistent with a cross-coupling reaction. For both com..

View full abstract

University of Melbourne Researchers