Department Lecture Series
Thursday February 14, 9:45 am, Smith 331

Discrete Late Metal Nitrenes in Catalytic C-H Amination

Catalytic C-H amination offers the opportunity to directly convert C-H bonds into amine functionalities without the need for prior chemical modification of these normally unreactive C-H bonds. Electrophilic, late transition metal-nitrene complexes [M]=NR are believed to be the active intermediates in this challenging transformation, providing greater chemoselectivity than free nitrenes themselves. Using well-defined ?-diketiminato complexes of Co, Ni, and Cu, we demonstrate the syntheses of discrete metal-nitrene complexes which enables a detailed examination of their electronic structure as well as reactivity towards a variety of substrates. These inorganic synthetic studies lead to the rational development of a catalytic system capable of inserting organoazides into a wide range of sp3-hybridized C-H bonds.

Leading References:
(1) “Transient Terminal Cu-Nitrene Intermediates from Discrete Dicopper Nitrenes” Badiei, Y. M.; Krishnaswamy, A.; Melzer, M.; Warren, T. H. J. Am. Chem. Soc. 2006, 128, 15056-15057.
(2) “A Terminal Ni(III)-Imide with Diverse Reactvity Pathways” Kogut, E.; Wiencko, H. L.; Zhang, L.; Cordeau, D. C.; Warren, T. H.* J. Am. Chem. Soc. 2005, 127, 11248-11249.