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Article Dans Une Revue Chemistry - A European Journal Année : 2023

Base‐Triggered Oxidative Addition to Gold

Résumé

The coordination of secondary phosphine oxides (SPO) was shown to efficiently promote the activation of C(sp2)−I bonds by gold, as long as a base is added (NEt3, K2CO3). These transformations stand as a new type of chelation-assisted oxidative addition to gold. The role of the base and the influence of the electronic properties of the P-ligand were analyzed computationally. Accordingly, the oxidative addition was found to be dominated by Au→(Ar−I) backdonation. In this case, gold behaves similarly to palladium, suggesting that the inverse electron flow reported previously (with prevailing (Ar−I)→Au donation, resulting in faster reactions of electron-enriched substrates) is a specific feature of electron-deficient cationic gold(I) complexes. The reaction gives straightforward access to (P=O,C)-cyclometallated Au(III) complexes. The possibility to chemically derivatize the SPO moiety at Au(III) was substantiated by protonation and silylation reactions.
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Dates et versions

hal-04110845 , version 1 (26-06-2023)

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Enrico Marelli, Julien Monot, Blanca Martin-Vaca, Sonia Mallet-Ladeira, Yago García-Rodeja, et al.. Base‐Triggered Oxidative Addition to Gold. Chemistry - A European Journal, 2023, pp.e202301091. ⟨10.1002/chem.202301091⟩. ⟨hal-04110845⟩
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