The moderately air-stable, six-coordinateruthenium nitrosyl porphyrin compounds, (T(p-OMe)PP)Ru(NO)(OC6HF4) and (T(p-OMe)PP)Ru(NO)(OC(=O)CF3) (T(p-OMe)PP = 5, 10, 15, 20-tetra(p-methoxyphenyl)porphinato dianion) have been prepared in good yields.  They have been characterized by IR and NMR spectroscopy, and X-ray crystallography. Their crystal structures contain near-linear RuNO moieties. The compounds are potential structural models of heme catalase and abnormal hemoglobin mutants associated with methemoglobemia. Cyclic voltammetry of the compounds reveal that they each undergo reversible one-electron first oxidations. (T(p-OMe)PP)Ru(NO)(OC6HF4) undergoes a reversible reduction whereas (T(p-OMe)PP)Ru(NO)(OC(=O)CF3) undergoes a partially reversible reduction in dichloromethane. The infrared spectroelectrochemistry of the compounds suggests porphyrin-centered first oxidations and competitive loss of both axial ligands after reduction.

Six-coordinate ruthenium nitrosyl porphyrins with carboxylate and aryloxide ligands: Preparation and redox behavior

245th National Meeting (2013)

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