Observation of Binuclear Palladium Clusters upon ESI-MS Monitoring of the Suzuki–Miyaura Cross-Coupling Catalyzed by a Dichloro-bis(aminophosphine) Complex of Palladium

Electrospray ionization mass spectrometry (ESI-MS) is used for monitoring the progress of the Suzuki–Miyaura cross-coupling reaction between bromobenzene and arylboronic acids using a palladium dichloro-bis(aminophosphine) complex as a precatalyst. The ESI-MS studies demonstrate that initiation of the catalytic reaction requires the presence of a base and that the selectivity for cross-coupling is favorable at elevated temperatures. Interestingly, after completion of the coupling reaction, the palladium is present as a dinuclear Pd 0 /Pd II cluster, which still acts as an active catalyst when a new aliquot of reactants is added to the reaction mixture.