Comparison of the Spectroscopically Measured Catalyst Transformation and Electrochemical Properties of Grubbs' First-...

According to UV-vis spectroscopy (0.10 mM, CH₂Cl₂ at 25 °C), the catalyst transformation (which could possibly include ligand dissociation with active catalyst formation, dimer formation, and decomposition) rate constants (k _obs) of Grubbs' first (1) and second (2) generation catalysts are 7.48 × 10^-5 and 1.52 × 10^-4 s^-1, respectively. From ³¹P NMR (0.1 M, CD₂Cl₂, at 25 °C), the catalyst transformation was 5.1% for 1 and 16.5% for 2 after 72 h. However, due to the larger concentrations of the NMR samples compared to the UV-vis samples, the extent of transformation did not correspond. The oxidation potential of the Ru^II/Ru^III couple of 2 (E°' = 27.5 mV at v = 200 mV s^-1) was considerably lower than that of 1 (E°' = 167 mV at v = 200 mV s^-1). In the case of 1, a second reduction peak appeared at slow scan rates. This may probably be ascribed to an electrochemically active compound that was formed from the intermediate cation 1 ^•+ and the subsequent reduction of the latter. The oxidation/reduction of 1 proceeds according to an E_rC_i electrochemical mechanism (E_r = electrochemically reversible step, C_i = chemically irreversible step), whereas 2 proceeds according to an E_rC_r electrochemical mechanism (E_r = electrochemically reversible step, C_i = chemically reversible step).