Carbon–Phosphorus Coupling from C^N Cyclometalated Au III Complexes

Riccardo Bonsignore , Sophie R Thomas , Wim T Klooster , Simon J Coles , Robert L Jenkins , Didier Bourissou (1) , Giampaolo Barone , Angela Casini

1 LHFA - Laboratoire Hétérochimie Fondamentale et Appliquée

With the aim of exploiting new organometallic species for cross-coupling reactions, we report here on the Au(III)-mediated Caryl-P bond formation occurring upon reaction of C^N cyclometalated Au(III) complexes with phosphines. The [Au(C^N)Cl2] complex 1 featuring the bidentate 2-benzoylpyridine (C CO N) scaffold was found to react with PTA (1,3,5-triaza-7-phosphaadamantane) under mild conditions, including in water, to afford the corresponding phosphonium 5 via C-P reductive elimination. A mechanism is proposed for the title reaction based on in situ 31 P{ 1 H} NMR and HR-ESI-MS analyses combined with DFT calculations. The C-P coupling has been generalized to other C^N cyclometalated Au(III) complexes and other tertiary phosphines. Overall, this work provides new insights into the reactivity of cyclometalated Au(III) compounds and establishes initial structure-activity relationships to develop Au(III)-mediated C-P cross-coupling reactions.

Mots clés: gold(III) cyclometalataled compounds; reductive elimination; cross- coupling; carbon-phosphorous bond; DFT

Domaines: Chimie

Riccardo Bonsignore, Sophie R Thomas, Wim T Klooster, Simon J Coles, Robert L Jenkins, et al.. Carbon–Phosphorus Coupling from C^N Cyclometalated Au III Complexes. Chemistry - A European Journal, 2020, 26 (19), pp.4226-4231. ⟨10.1002/chem.201905392⟩. ⟨hal-03005616⟩