Structures and Reactivity of Group 9 Metalloporphyrin Complexes
Our current work focuses on group 9 (Rh, Ir) metalloporphyrins. This includes probing the reactivity of coordination complexes and determining the structures of the subsequent products.3 Recently, tetratolylporphyrinato (TTP) methyliridium, Ir(TTP)CH3, was shown to be an active and robust catalyst for the cyclopropanation of olefins using diazo reagents as carbene sources.4 Ir(TTP)CH3 also catalyzes N–H insertion reactions between ethyl diazoacetate (EDA) or methyl phenyldiazoacetate (MPDA) and a variety of aryl, aliphatic, primary, and secondary amines.5 Reactions with aryl amines produce the highest yields with up to 105 catalyst turnovers and without the need for slow addition of the diazo reagent. Mechanistic aspects of diazo insertion reactions are examined. In addition, a comparison of the molecular structures of RhIII(TTP) and IrIII(TTP) carbene complexes provides insights for understanding reactivity differences for the two metals complexes.6
1. Anding, B. J.; Woo, L. K. In Handbook of Porphyrin Science; Kadish, K. M., Guilard, R., Smith, K., Eds.; World Scientific Publishing Company: Hackensack, NJ, 2012; Vol. 21, p 145.
2. Mirafzal, G. A.; Cheng, G.; Woo, L. K. J. Am. Chem. Soc. 2002, 124, 176-177.
3. Dairo, T. O.; Ellern, A.; Angelici, R. J.; Woo, L. K. Organometllics, 2014, 33, 2266-2276.
4. Anding, B. J.; Ellern, A.; Woo, L. K. Organometallics 2012, 31, 3628-3635.
5. Anding, B. J.; Woo, L. K. Organometallics, 2013, 32, 2599-2607.