The palladium(II) aqua complex [Pd(PNP)(H2O)](SbF6)2 can be prepared either from [Pd(PNP)Cl]Cl and silver hexafluoroantimonate in the presence of water or by substitution of ethylene in [Pd(PNP)(C2H2)](SbF6)2 by water. The auqa complex shows the same catalytic activity as the previously studied ethylene complex [Pd(PNP)(C2H4)](SbF6)2 for the addition of pentamethylbenzene to acetylene. Arenes with higher nucleophilicity than pentamethylbenzene such as 1,3,5-trimethoxybenzene would add to the coordinated ethylene in the pre-catalyst prior substitution of ethylene by acetylene. This caused deactivation of the catalyst by formation of a stable σ-alkyl complex. The aqua complex has been identified as promising pre-catalyst for two reasons: (1) strongly nucleophilic arenes may not react with the aqua ligand, and (2) the water itself serves as an efficient co-catalyst. With the aqua complex [Pd(PNP)(H2O)](SbF6)2 the scope of arene substrates has been explored.

Dicationic palladium(II) aqua complex as new catalyst for the hydroarylation of acetylene

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