Catalyst selection: survival of the weakest


ADF calculations support a new mass spectrometric method to select the best catalysts from a combinatorial library in a combined experimental-theoretical study.

The turnover frequency determining step for the Pd-catalyzed allylic alkylation is the nucleophilic attack on the Pd-allyl intermediate. Destabilizing this intermediate decreases the activation energy, thus improving the catalyst. Consequently, the least abundant Pd-allyl complex in the ESI-MS spectrum is the most active catalyst: ‘survival of the weakest’. The DFT calculations are in agreement with the experiments: larger bite angles increase the steric congestion and thus strain at Pd, destabilizing the diphosphino-Pd-allyl complex, leading to lower MS abundance and a higher TOF.

Catalyst Selection: survival of the weakest

Destabilizing the Pd-allyl intermediate enhances catalytic allylic alkylation.

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