A Mechanistic Investigation Of The Suzuki Polycondensation Reaction Using Ms/Ms Methods

Understanding catalytic reactions is inherently difficult because not only is the catalyst the least abundant component in the mixture, but it also takes many different forms as the reaction proceeds. Precatalyst is converted into active catalyst, short-lived intermediates, resting states, and decomposition products. Polymerization catalysis is harder yet to study, because as the polymer grows the identities of these species change with every turnover as monomers are added to the chain. Modern mass spectrometric methods have proved to be up to the challenge, with multiple reaction monitoring (MRM) in conjunction with pressurized sample infusion (PSI) used to continuously probe all stages of the Suzuki polycondensation (SPC) reaction. Initiation, propagation, and termination steps were tracked in real time, as well as the side products from undesirable aryl-phosphine scrambling. The outstanding sensitivity and low signal-to-noise of the approach has real promise with respect to the depth with which this reaction and others like it can be studied.