Aqueous-Phase Chemistry of η 3 -Allylpalladium(II) Complexes with Sulfonated N -Heterocyclic Carbene Ligands : Solvent Effects in the Protolysis of Pd–C Bonds and Suzuki–Miyaura Reactions Article - 2017

Juan Manuel Asensio, Roman Andres, Pilar Gómez-Sal, Ernesto de Jesus

Juan Manuel Asensio, Roman Andres, Pilar Gómez-Sal, Ernesto de Jesus, « Aqueous-Phase Chemistry of η 3 -Allylpalladium(II) Complexes with Sulfonated N -Heterocyclic Carbene Ligands : Solvent Effects in the Protolysis of Pd–C Bonds and Suzuki–Miyaura Reactions  », Organometallics, 2017, pp. 4191-4201. ISSN 0276-7333

Abstract

The synthesis of water-soluble η 3-allyl Pd(II) complexes containing sulfonated N-heterocyclic carbene (NHC) ligands of general formula [Pd(NHC) n (η 3-allyl)Cl 2−n ] is reported (n = 1 (1) or 2 (8)). Monocarbene complexes were obtained with the most sterically hindered NHC ligands, and biscarbenes with the less sterically hindered NHCs. The behavior of the isolated complexes in water under acidic, neutral, or alkaline conditions has been studied. The complexes are rather stable in water under neutral or alkaline conditions, although displacement of the chlorido ligand by water or hydroxide occurs under these conditions. In acidic media, Pd−NHC bonds are protolysed, and it is especially noteworthy that this protolysis occurs preferentially to that of the Pd−allyl bonds in the case of the complexes with the less-sterically hindered NHC ligands. This behavior contrasts with that observed in dimethyl sulfoxide (dmso), where the Pd− allyl bonds are selectively broken upon treatment with Brö nsted acids. In addition, Pd−NHC bond breaking was promoted by the addition of a strong σ-donor ligand such as cyanide. Complex 1a is an active catalyst for the Suzuki−Miyaura cross-coupling of water-soluble aryl chlorides in neat water under moderate conditions (typically, 0.5 mol % Pd and 60 °C).

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