Ligand fluorination to optimize preferential oxidation of carbon monoxide by water-soluble rhodium porphyrins

Justin C. Biffinger, Shriharsha Uppaluri, Haoran Sun, Stephen G. Dimagno

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

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 (pKa = 2.2 ± 0.2 for 2[Rh-D]); the dramatically increased acidity of the Rh(III) hydride complex precludes proton reduction and hydrogen activation near neutral pH, thereby permitting oxidation of CO to be unaffected by the presence of H2. This new fluorinated water-soluble rhodium porphyrin-based homogeneous catalyst system permits preferential oxidation of carbon monoxide in hydrogen gas streams at 308 K using dioxygen or a sacrificial electron acceptor (indigo carmine) as the terminal oxidant.

Original languageEnglish (US)
Pages (from-to)764-771
Number of pages8
JournalACS Catalysis
Volume1
Issue number7
DOIs
StatePublished - Jul 1 2011

Fingerprint

Fluorination
Rhodium
Porphyrins
Carbon Monoxide
Carbon monoxide
Ligands
Oxidation
Water
Acidity
Hydrides
Hydrogen
Salts
Indigo Carmine
Oxidants
Reaction rates
Protons
Gases
Metals
Chemical activation
Oxygen

Keywords

  • Rhodium
  • carbon monoxide
  • fluorinated macrocycle
  • fuel cells
  • oxidation
  • porphyrin

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

Ligand fluorination to optimize preferential oxidation of carbon monoxide by water-soluble rhodium porphyrins. / Biffinger, Justin C.; Uppaluri, Shriharsha; Sun, Haoran; Dimagno, Stephen G.

In: ACS Catalysis, Vol. 1, No. 7, 01.07.2011, p. 764-771.

Research output: Contribution to journalArticle

Biffinger, Justin C. ; Uppaluri, Shriharsha ; Sun, Haoran ; Dimagno, Stephen G. / Ligand fluorination to optimize preferential oxidation of carbon monoxide by water-soluble rhodium porphyrins. In: ACS Catalysis. 2011 ; Vol. 1, No. 7. pp. 764-771.
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