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 PhINTs aziridination/amidation of hydrocarbons, and intramolecular amidation of sulfamate esters with PhI(OAc) 2 . Oxidation of PEG‐ 1 by m ‐CPBA in CH 2 Cl 2 , 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 k 2 values at a water content of 70 % or 80 % are up to 188 times that obtained in ClCH 2 CH 2 Cl.