Catalysis


Metals exist in solution coordinated to to form , which can act as for important chemical transformations. Among most ubiquitous classes of ligands are Î²-diketonates, of which the ligand acetylacetonate or "acac" is the most common. are widely used in a variety of important chemical applications; however, their use in catalysis is limited because they tend to form complexes that are , meaning that they don't easily permit substrates to bind. 

We have designed and synthesized a series of Î²-diketonate ligands that are functionalized with large m-terphenyl groups that prevent coordinative saturation at the metal. These new ligands provide a platform for detailed investigations into catalytic mechanisms that should help us discover and optimize new catalytic chemical transformations that could have an impact in the synthesis of organic chemicals. Î²-diketonate ligands coordinate to metals in vastly different ways than other ligands that have been investigated. In particular, they are weak σ-bond donors like water, but strong Ï€-acceptors, like cyanide. This provides a unique electronic environment that could open the door to discovery of new reactivity and chemical transformations.


Hopkins, E. J.; Krajewski, S. M.; Crossman, A. S.; Maharaj, F. D. R.; Schwanz, L. T.; Marshak, M. P. . Eur. J. Inorg. Chem. 2020, 20, 1951–1959.

Larson, A. T.; Crossman, A. S.; Krajewski, S. M.; Marshak, M. P. . Inorg. Chem. 202059, 423–432.

Krajewski, S. M.; Crossman, A. S.; Akturk, E. S.; Suhrbier, T.; Scappaticci, S. J.; Staab, M. W.; Marshak, M. P. . Dalton Trans. 201948, 10714–10722.

Crossman, A. S.; Larson, A. T.; Shi, J. X.; Krajewski, S. M.; Akturk, E. S.; Marshak, M. P. . J. Org. Chem201984 (11), 7434–7442.

Akturk, E. S.; Scappaticci, S. J.; Seals, R. N.; Marshak, M. P. . Inorg. Chem.2017, 56 (19), 11466–11469.