Fast time-resolved infrared spectroscopic measurements have allowed precise determination of the reaction rates for the C-H activation of alkanes in Cp-Rh(H)(CO)(alkane) and Cp*-Rh(H)(CO)(alkane) [alkane = cyclopentane, cyclohexane and neopentane]. To further understand the rate of these reactions, theoretical calculations were conducted with the same complexes but with Ir substituted for Rh metal center. Density functional theory was used to calculate electronic and free energies for the separated species, intermediates, and transition states for the mechanism. The calculations determined that the Cp-Ir complexes had lower activation barriers and therefore have a faster reaction rate than the Cp-Rh complexes. However, the Cp*-Ir complexes have higher activation barriers, which causes them to react slower than their Cp*-Rh counterparts.

C-H activation of Cp-Ir(RH)(CO) and Cp*-Ir(RH)(CO)

247th National Meeting (2014)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.