The photochemical C-H activation reactions of η3-Tp*Rh(CO)2 (Tp* = HB-Pz3*, Pz* = 3,5-dimethylpyrazolyl) and CpRh(CO)2 (Cp = C5H5) have been studied in a series of linear, cyclic, and aromatic hydrocarbon solvents on a femtosecond to microsecond time scale. These results have revealed that the structure of the hydrocarbon substrate affects the final C-H bond activation step, which is in accordance with the known preference of bond activation toward primary C-H sites. In the case of aromatic C-H activation, the reaction is divided into parallel channels involving σ- and π-solvated intermediates. Results for the analogous CpRh(CO)2 molecule have shown that the coordination of the cyclopentadienyl ligand does not play a direct role in the dynamics of the reaction, in contrast to the C-H activation mechanism observed in η3-Tp*Rh(CO)2 studies.
All Science Journal Classification (ASJC) codes
- Colloid and Surface Chemistry