Donor-Flexible Bis(pyridylidene amide) Ligands for Highly Efficient Ruthenium-Catalyzed Olefin Oxidation.

An exceptionally efficient ruthenium-based catalyst for olefin oxidation has been designed by exploiting N,N'-bis(pyridylidene)oxalamide (bisPYA) as a donor-flexible ligand. The dynamic donor ability of the bisPYA ligand, imparted by variable zwitterionic and neutral resonance structure contributions, paired with the redox activity of ruthenium provided catalytic activity for Lemieux-Johnson-type oxidative cleavage of olefins to efficiently prepare ketones and aldehydes. The ruthenium bisPYA complex significantly outperforms state-of-the-art systems and displays extraordinary catalytic activity in this oxidation, reaching turnover frequencies of 650 000 h and turnover numbers of several millions.