51669-90-0Relevant academic research and scientific papers
Electrochemical and spectroelectrochemical studies of monomeric rhodium (III) porphyrins in nonaqueous media
Kadish,Yao,Anderson,Cocolios
, p. 4515 - 4520 (2008/10/08)
The electrochemistry and spectroelectrochemistry of (TPP)Rh(NH(CH3)2)Cl and (TPP)Rh(NH(CH3)2)2+Cl- were investigated in benzonitrile, THF, and pyridine. In benzonitrile, both of these six-coordinated Rh(III) complexes undergo two reductions and two oxidations at room temperature. No oxidations are observed in THF or pyridine (due to the limited solvent window), but two reductions are observed for the two complexes in each of these solvents. The first reduction is followed by a rapid chemical reaction, which generates a diamagnetic species that appears to be a rhodium(II) dimer. The second reduction is a two-electron reaction that produces another diamagnetic species. Electronic absorption spectra indicate the second reduction is at the porphyrin π system. The two oxidations generate the cation radical and dication of the Rh(III) compounds and give electronic absorption and ESR spectra similar to those of other metalloporphyrin π radical cations and dications. On the basis of the electrochemical and spectroscopic results, an overall oxidation-reduction scheme was formulated.
