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Direct intramolecular carbon(sp2)-nitrogen(sp2) reductive elimination from gold(III)

par Kim, Jong Hyun;Mertens, Tyler R.T.;Agarwal, Amal;Parkin, Sean R.;Berger, Gilles ;Awuah, Samuel S.G.
Référence Dalton transactions, 48, 18, page (6273-6282)
Publication Publié, 2019-04-01

Article révisé par les pairs

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Résumé :

The reactivity of bidentate Au III -Cl species, [(C^N)AuCl 2 ], with a bisphosphine or carbon donor ligands results in reductive elimination. Combined experimental and computational investigations lead to the first evidence of a direct intramolecular C(sp 2 )-N(sp 2 ) bond formation from a monomeric [(C^N)AuCl 2 ] gold(iii) complex. We show that bidentate ligated Au(iii) systems bypass transmetallation to form C(sp 2 )-N(sp 2 ) species and NHC-Au-Cl. Mechanistic investigations of the reported transformation reveal a ligand-induced reductive elimination via a key Au III intermediate. Kinetic studies of the reaction support a second-order rate process.