4:30pm - 5:30pm
Room 209 Havemeyer
New York, NY 10027
Abstract. Cp*Rh(III) complexes have emerged as a powerful mode of catalysis for C-H activation transformations providing a broad spectrum of reactivity. The tremendous efforts devoted to exploring the scope available with Cp*Rh(III) catalysts have somewhat obscured the search for alternative cyclopentadienyl based ligands. The design of a new set of ligands for rhodium has shown a significant amount of success in solving inherent problems of reactivity and selectivity encountered throughout the development of new Rh(III)-catalyzed transformations. This presentation will describe the evolution of cyclopentadienyl ligand skeletons in Rh(III)-catalysis. Specific emphasis is placed on reactivity and synthetic applications achieved with the new ligands with the introduction of achiral mono-, di-, or pentasubstituted cyclopentadiene ligands exhibiting a stunning effect on reactivity and selectivity.1,2 Furthermore, an underlying question when dealing with ligand modification strategies is why one ligand outperforms another. Conjecture and speculation abound, but extensive characterization of their steric and electronic properties has been carried out and information about electronic and steric properties of the ligands all contribute to our understanding and give crucial pieces for the puzzle to be pieced together.3
1 Piou, T.; Rovis, T. J. Am. Chem. Soc. 2014, 136, 11292.
2 Piou, T.; Rovis, T. Nature 2015, 527, 86.
3 Piou, T.;§ Romanov-Michailidis, F.;§ Romanova-Michaelides, M.; Jackson, K.; Semakul, N.; Taggart, T. R.; Paton, R. S.; Rovis, T. Manuscript in preparation (§Authors contributed equally).
Department of Chemistry, Columbia University, Havemeyer Hall, 3000 Broadway, New York, NY 10027, USA | 212-854-2202 | http://chem.columbia.edu/