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Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
Palladium mono-N-protected amino acid complexes: experimental validation of the ligand cooperation model in C-H
Sara Fernández-Moyano1, Vanesa Salamanca1, Ana C Albéniz1
1IU CINQUIMA/Química Inorgánica, Universidad de Valladolid 47071-Valladolid Spain albeniz@uva.es.
Abstract:
Mechanistic proposals for the C-H activation reaction enabled by mono-N-protected amino acid ligands (MPAAs) have been supported by DFT calculations. The direct experimental observation of the ligand-assisted C-H activation has not yet been reported due to the lack of well-defined isolated palladium complexes with MPAAs that can serve as models. In this work, palladium complexes bearing chelating MPAAs (NBu4)[Pd(κ2-N,O-AcN-CHR-COO)(C6F5)py] (Ac = MeC(O); R = H, Me) and [Pd(κ2-N,O-MeNH-CH2-COO)(C6F5)py] have been isolated and characterized. Their evolution in a solution containing toluene leads to the C-H activation of the arene and the formation of the C6F5-C6H4Me coupling products. This process takes place only for the ligands with an acyl protecting group, showing the cooperating role of this group in a complex with a chelating MPAA, therefore experimentally validating this working model. The carboxylate group is inefficient in this C-H activation.
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