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- W2074336871 abstract "The photochemical water gas shift reaction (WGSR) catalyzed, under mild conditions (25[degrees]C, 1 atm CO, visible light, pH = 7), by [([eta][sup 5]-Me[sub 5]C[sub 5])Ir[sup III](bpy)X][sup +] (bpy = 2,2[prime]-bipyridine, X = H, Cl), [([eta][sup 5]-Me[sub 5]C[sub 5])Ir[sup III](phen)X][sup +] (phen = 1,10-phenanthroline, X = H, Cl), or [([eta][sup 5]-Me[sub 5]C[sub 5])Ir[sup III](bpyRR[prime])Cl][sup +] (R = R[prime] = COOH, COOiPr, Br, NO[sub 2], NMe[sub 2] in the 4,4[prime]-positions or R = R[prime] = COOH, R = H and R[prime] = SO[sub 3]H in the 5,5[prime]-positions of the bpy ligand) has been investigated. A turnover frequency for H[sub 2] formation of 32 h[sup [minus]1] was obtained in an aqueous phosphate buffer containing [([eta][sup 5]-Me[sub 5]C[sub 5])Ir[sup III](bpy-4,4[prime]-(COOH)[sub 2]Cl)][sup +] as catalyst, over a 7-h irradiation period at a constant CO pressure of 1 atm. An increase of 1 order of magnitude in catalytic activity was observed for the bpy ligand substituted with two carboxylate groups in the 4,4[prime]- or 5,5[prime]-positions or with one sulfonate group in the 5-position (over the nonsubstituted bpy equivalent). Conversely, catalytic activity was lost when the bpy was substituted with two dimethylamino groups. The presence of an electron withdrawing group on the bpy-chelate was shown to decreasemore » the activation energy of the process (E[sub a] = 14.6 kJ mol[sup [minus]1] for R = COOH, E[sub a] = 22.2 kJ mol[sup [minus]1] for R = COOiPr), cf. the unsubstituted ligand (E[sub a] = 29.6 kJ mol[sup [minus]1] for R = H). 64 refs., 8 figs., 5 tabs.« less" @default.
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- W2074336871 date "1993-01-01" @default.
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- W2074336871 title "Photocatalysis. Mechanistic studies of homogeneous photochemical water gas shift reaction catalyzed under mild conditions by novel cationic iridium(III) complexes" @default.
- W2074336871 doi "https://doi.org/10.1021/ja00054a017" @default.
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