Nucleophilic Addition To Pi-Allyl Gold(Iii) Complexes: Evidence For Direct And Undirect Paths

pi-Allyl complexes play a prominent role in organometallic chemistry and have attracted considerable attention, in particular the pi-allyl Pd(II) complexes which are key intermediates in the Tsuji-Trost allylic substitution reaction. Despite the huge interest in pi-complexes of gold, pi-allyl Au(III) complexes were only authenticated very recently. Herein, we report the reactivity of (P,C)-cyclometalated Au(III) pi-allyl complexes toward beta-diketo enolates. Behind an apparently trivial outcome, i.e. the formation of the corresponding allylation products, meticulous NMR studies combined with DFT calculations revealed a complex and rich mechanistic picture. Nucleophilic attack can occur at the central and terminal positions of the pi-allyl as well as the metal itself. All paths are observed and are actually competitive, whereas addition to the terminal positions largely prevails for Pd(II). Auracyclobutanes and pi-alkene Au(I) complexes were authenticated spectroscopically and crystallographically, and Au(III) sigma-allyl complexes were unambiguously characterized by multinuclear NMR spectroscopy. Nucleophilic additions to the central position of the pi-allyl and to gold are reversible. Over time, the auracyclobutanes and the Au(III) sigma-allyl complexes evolve into the pi-alkene Au(I) complexes and release the C-allylation products. The relevance of auracyclobutanes in gold-mediated cyclopropanation was demonstrated by inducing C-C coupling with iodine. The molecular orbitals of the pi-allyl Au(III) complexes were analyzed in-depth, and the reaction profiles for the addition of beta-diketo enolates were thoroughly studied by DFT. Special attention was devoted to the regioselectivity of the nucleophilic attack, but C-C coupling to give the allylation products was also considered to give a complete picture of the reaction progress.