@article {2228, title = {Synthetic and mechanistic aspects of a new method for ruthenium-metalation of porphyrins and Schiff-bases}, journal = {Inorganic Chemistry}, volume = {47}, number = {17}, year = {2008}, note = {ISI Document Delivery No.: 341JDTimes Cited: 3Cited Reference Count: 266Reboucas, Julio S. Cheu, Elizabeth L. S. Ware, Caroline J. James, Brian R. Skov, Kirsten A.}, month = {Sep}, pages = {7894-7907}, type = {Review}, abstract = {A new method is presented for metalation of a wide range of free-base, neutral, cationic, and anionic porphyrins in refluxing dimethylformamide (DMF) using an easily prepared [Ru(DMF)(6)](OTf)(3) complex, and comparisons are made with the more familiar metalation procedure using Ru-3(CO)(12). Both procedures generate Ru-II(porp)(CO)L complexes (L = solvent); use of the Ru-III-triflate precursor gives yields comparable to, or greater than, those obtained with the carbonyl, and generates no Ru-chlorin impurities. Mechanistic studies on the meso-tetraphenylporphyrin system reveal that the DMF furnishes the CO, which in the presence of essential water reduces the metal, and metalation likely occurs via a Ru-II-CO species. Corresponding metalation of tetradentate Schiff-bases gives trans-[Ru-III(Schiff-base)(DMF)(2)]OTf complexes in yields of similar to 50\%, a limitation being the accompanying hydrolysis of the Schiff-base through the presence of trace water.}, keywords = {3-COMPONENT COUPLING REACTION, AQUEOUS-SOLUTION, CARBON-MONOXIDE, CATALYTIC-PROPERTIES, CRYSTAL-STRUCTURE, ELECTROCHEMICAL PROPERTIES, ORGANIC TRANSFORMATIONS, OXIDATION REACTION, REVERSIBLE BINDING, X-RAY-STRUCTURE}, isbn = {0020-1669}, url = {://000258709500057}, author = {Reboucas, J. S. and Cheu, E. L. S. and Ware, C. J. and James, Brian R. and Skov, K. A.} }