Oxidation Reactivity of a Structurally and Spectroscopically Well-defined Mononuclear Peroxocarbonato-Iron(III) Complex

Tsugawa T; Furutachi H; Marunaka M; Endo T; Hashimoto K; Fujinami S; Akine S; Sakata Y; Nagatomo S; Tosha T; Nomura T; Kitagawa T; Ogura T; Suzuki M

Chemistry Letters, Vol.44, No.3, 330-332, 2015

Tsugawa T, Furutachi H, Marunaka M, Endo T, Hashimoto K, Fujinami S, Akine S, Sakata Y, Nagatomo S, Tosha T, Nomura T, Kitagawa T, Ogura T, Suzuki M

A mononuclear peroxocarbonato-iron(III) complex [Fe-(6Me-pic)(2)(O2C(O)O)](-) (1-O2C(O)O) with bidentate ligands (6Me-pic), prepared by the reaction of a carbonato-iron(III) complex [Fe(6Me-pic)(2)(CO3)(-) (1-CO3) with H2O2, was fully characterized. 1-O2C(O)O showed reversible O-O bond cleavage and reformation of the peroxo group under CO2 at 25 degrees C. 1-O2C(O)O is capable of not only oxidizing the C=C bond of cyclooctene but also the C-H bond of toluene. As for cyclooctene, epoxidation is favorable under CO2 in the presence of H2O, while cis-dihydroxylafion precedes under N-2, indicating that the oxidation reactivity of 1-O2C(O)O toward cyclooctene can be tuned by changing the concentration of CO2 and H2O.