Synthetic and mechanistic aspects of a new method for ruthenium-metalation of porphyrins and Schiff-bases.
作者： Júlio S. Rebouças , Elizabeth L. S. Cheu , Caroline J. Ware , Brian R. James , Kirsten A. Skov
DOI: 10.1021/IC800616Q
关键词:
摘要: A new method is presented for metalation of a wide range free-base, neutral, cationic, and anionic porphyrins in refluxing dimethylformamide (DMF) using an easily prepared [Ru(DMF)6](OTf)3 complex, comparisons are made with the more familiar procedure Ru3(CO)12. Both procedures generate RuII(porp)(CO)L complexes (L = solvent); use RuIII-triflate precursor gives yields comparable to, or greater than, those obtained carbonyl, generates no Ru-chlorin impurities. Mechanistic studies on meso-tetraphenylporphyrin system reveal that DMF furnishes CO, which presence essential water reduces metal, likely occurs via RuII−CO species. Corresponding tetradentate Schiff-bases trans-[RuIII(Schiff- base)(DMF)2]OTf ∼50%, limitation being accompanying hydrolysis Schiff-base through trace water.
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