. . . "Samec, Zden\u011Bk" . "Inhibitory Effect of Water on the Oxygen Reduction Catalyzed by Cobalt(II) Tetraphenylporphyrin"@en . . "21857" . "000333381700006" . . "Inhibitory Effect of Water on the Oxygen Reduction Catalyzed by Cobalt(II) Tetraphenylporphyrin" . . . . "Stopped- fl ow kinetic measurements, UV vis spectroscopy, rotating disk voltammetry, and quantum chemical calculations are used to clarify the role of water in the homogeneous two-electron reduction of O 2 to H 2 O 2 in 1,2-dichloroethane (DCE) using ferrocene (Fc) as an electron donor, tetrakis(penta fl uorophenyl)boric acid (HTB) as a proton donor, and [5,10,15,20-tetraphenyl-21 H ,23 H - porphine]cobalt(II) (Co II TTP) as a catalyst. Kinetic analysis suggests that the reaction is controlled by the intramolecular proton coupled electron transfer to the O 2 molecule coordinated to the metal center producing the O 2 H radical. This rate- determining step is common to both the O 2 reduction by Fc catalyzed by Co II TPP and the O 2 reduction by Co II TPP itself. Experimental data point to the competitive coordination of water to the metal center leading to a strong inhibition of the catalytic reaction. In agreement with this finding, quantum chemical calculations indicate that water is bound to the metal center much more strongly than triplet O2. A similar effect is demonstrated also for the O2 reduction catalyzed by the porphyrin free base (H2 TPP), though its rate is lower by 2 orders of magnitude."@en . "5"^^ . "118" . . "Stopped- fl ow kinetic measurements, UV vis spectroscopy, rotating disk voltammetry, and quantum chemical calculations are used to clarify the role of water in the homogeneous two-electron reduction of O 2 to H 2 O 2 in 1,2-dichloroethane (DCE) using ferrocene (Fc) as an electron donor, tetrakis(penta fl uorophenyl)boric acid (HTB) as a proton donor, and [5,10,15,20-tetraphenyl-21 H ,23 H - porphine]cobalt(II) (Co II TTP) as a catalyst. Kinetic analysis suggests that the reaction is controlled by the intramolecular proton coupled electron transfer to the O 2 molecule coordinated to the metal center producing the O 2 H radical. This rate- determining step is common to both the O 2 reduction by Fc catalyzed by Co II TPP and the O 2 reduction by Co II TPP itself. Experimental data point to the competitive coordination of water to the metal center leading to a strong inhibition of the catalytic reaction. In agreement with this finding, quantum chemical calculations indicate that water is bound to the metal center much more strongly than triplet O2. A similar effect is demonstrated also for the O2 reduction catalyzed by the porphyrin free base (H2 TPP), though its rate is lower by 2 orders of magnitude." . "[04CC1B9F469C]" . . "5"^^ . "1089-5639" . . "electrochemistry; porphyrins; biomimetic catalysts"@en . "Langmaier, Jan" . . "Inhibitory Effect of Water on the Oxygen Reduction Catalyzed by Cobalt(II) Tetraphenylporphyrin"@en . "US - Spojen\u00E9 st\u00E1ty americk\u00E9" . . "Journal of Physical Chemistry A" . "Kvapilov\u00E1, Hana" . . "10.1021/jp500057x" . "I, P(GAP208/11/0697)" . "11"^^ . "Inhibitory Effect of Water on the Oxygen Reduction Catalyzed by Cobalt(II) Tetraphenylporphyrin" . . . . "RIV/61388955:_____/14:00427152!RIV15-GA0-61388955" . "Troj\u00E1nek, Anton\u00EDn" . "RIV/61388955:_____/14:00427152" . "11" . . "Z\u00E1li\u0161, Stanislav" . . .