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Ligand Fluorination To Optimize Preferential Oxidation Of Carbon Monoxide By Water-Soluble Rhodium Porphyrins, Justin C. Biffinger, Shriharsha Uppaluri, Haoran Sun, Stephen G. Dimagno

Stephen DiMagno Papers

Catalytic, low temperature preferential oxidation (PROX) of carbon monoxide by aqueous [5,10,15,20-tetrakis- (4-sulfonatophenyl)-2,3,7,8,12,13,17,18-octafluoroporphyrinato]- rhodium(III) tetrasodium salt, (1[Rh(III)]) and [5,10,15, 20-tetrakis(3-sulfonato-2,6-difluorophenyl)-2,3,7,8,12,13, 17,18-octafluoroporphyrinato]rhodium(III) tetrasodium salt, (2[Rh(III)]) is reported. The PROX reaction occurs at ambient temperature in buffered (4 ≤ pH ≤ 13) aqueous solutions. Fluorination on the porphyrin periphery is shown to increase the CO PROX reaction rate, shift the metal centered redox potentials, and acidify ligated water molecules. Most importantly, β-fluorination increases the acidity of the rhodium hydride complex (pK_a = 2.2 ± 0.2 for 2[Rh-D]); the dramatically increased acidity of the Rh(III) hydride complex precludes proton reduction …