The team of Prof. Steve Nolan and Prof. Catherine Cazin contributed to research on the ligand-directed reactivity in dioxygen and water to palladium systems. This research was published in the high-ranked Journal of the American Chemical Society.

Modification of the reaction chemistry of dioxygen by coordination to metal complexes is essential to biochemical catalysis and central to industrial oxidation chemistry. For example, heme coordination complexes containing an iron ion play an important role in the human body for the binding and transport of dioxygen from the lungs to other tissues. A recent overview of the chemistry of dioxygen states “The life forms that evolved subsequently must have evolved the way they did, in order to cope with, and utilize, molecular oxygen”. This evolution must include the development of an array of metallo-enzymes, enzyme proteins containing metal ions in which this metal ion plays an important role in the catalytic activity of the enzymes. Study of the binding of dioxygen to these larger and more complex bioinorganic molecules, such as heme, dates back to a seminal paper by Pauling and co-workers in 1936. To this day, aspects of this reaction remain a matter of active investigation. Study on the binding of dioxygen to simpler organometallic systems is important and may also provide insights into fundamental principles relevant for more complex systems.   

In this recent international collaboration, the model palladium systems developed by Ghent researchers are examined in a detailed study to probe the effects of the environment of the metal on dioxygen binding.

Reference to the full paper: J. Am. Chem. Soc. 2018, DOI 10.1021/jacs.7b09905

Ligan-directed reactivity in dioxygen and water binding to cis-[Pd(NHC)₂(η²-O₂)]
Taryn D. Pallucio, Xiaochen Cai, Subhojit Majumdar, Leonarda F. Serafim, Neil C. Tomson, Karl Weighardt, Catherine S. J. Cazin, Steven P. Nolan, Elena V. Rybak-Akimova, Miguel Ángel Fernández-González, Manuel Temperado, Burjor Captain and Carl D. Hoff