C–H Insertion Catalyzed by Tetratolylporphyrinato Methyliridium via a Metal–Carbene IntermediateOrganometallics
Publication VersionPublished Version
AbstractC–H insertion reactions between different substrates and diazo reagents were catalyzed by tetratolylporphyrinato methyliridium (Ir(TTP)CH3). The highest yields were achieved for reactions between the bulky diazo reagent methyl 2-phenyldiazoacetate (MPDA) and substrates containing electron-rich C–H bonds. An intermediate metalloporphyrin complex was identified as a metal–carbene complex, Ir(TTP)(═C[Ph]CO2CH3)(CH3) (4), using 1H NMR and UV/vis absorption spectroscopy. The presence of 4 was further supported by computationally modeling the absorption spectra with time-dependent DFT (6-31G(d,p)/SBKJC basis set, PBE0 functional). Kinetic studies for C–H insertion reactions using different substrates showed substantial differences in the rate of MPDA consumption, suggesting that carbene transfer is rate-limiting. Furthermore, primary kinetic isotope effects of 3.7 ± 0.3 and 2.7 ± 0.4 were measured using toluene and cyclohexane, respectively. These data are consistent with a mechanism that involves direct C–H insertion rather than a radical rebound pathway.
Copyright OwnerAmerican Chemical Society
Citation InformationBernie Anding, Jakoah Brgoch, Gordon J. Miller and L. Keith Woo. "C–H Insertion Catalyzed by Tetratolylporphyrinato Methyliridium via a Metal–Carbene Intermediate" Organometallics Vol. 31 Iss. 15 (2012) p. 5586 - 5590
Available at: http://works.bepress.com/l-woo/18/