Oxidation chemistry of poly(ethylene glycol)-supported carbonylruthenium(II) and dioxoruthenium(VI) meso-tetrakis(pentafluorophenyl)porphyrin

[Ru-II(F-20-tpp)(CO)] (1, F-20-tpp=meso-tetrakis(pentafluorophenyl)porphyrinato dianion) was covalently attached to poly(ethylene glycol) (PEG) through the reaction of 1 with PEG and sodium hydride in DMF. The water-soluble PEG-supported ruthenium porphyrin (PEG-1) is an efficient catalyst for 2,6-Cl(2)pyNO oxidation and PhI=NTs aziridination/amidation of hydrocarbons, and intramolecular amidation of sulfamate esters with PhI-(OAc)(2). Oxidation of PEGA by mCPBA in CH2Cl2, dioxane, or water afforded a water-soluble PEG-supported dioxoruthenium(vi) porphyrin (PEG-2). which could react with hydrocarbons to give oxidation products in up to 80 % yield. The behavior of the two PEG-supported ruthenium porphyrin complexes in water was probed by NMR spectroscopy and dynamic light-scattering measurements. PEG-2 is remarkably stable to water. The second-order rate constants (k(2)) for the oxidation of styrene and ethylbenzene by PEG-2 in dioxane-water increase with water content, and the k2 values at a water content of 70% or 80% are up to 188 times that obtained in ClCH2CH2Cl.