Cp*Co(III) catalysts with proton-responsive ligands for carbon dioxide hydrogenation in aqueous media

Yosra M. Badiei, Wan Hui Wang, Jonathan F. Hull, David J. Szalda, James Muckerman, Yuichiro Himeda, Etsuko Fujita

Research output: Contribution to journalArticle

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Abstract

New water-soluble pentamethylcyclopentadienyl cobalt(III) complexes with proton-responsive 4,4′- and 6,6′-dihydroxy-2,2′-bipyridine (4DHBP and 6DHBP, respectively) ligands have been prepared and were characterized by X-ray crystallography, UV-vis and NMR spectroscopy, and mass spectrometry. These cobalt(III) complexes with proton-responsive ligands predominantly exist in their deprotonated [Cp*Co(DHBP-2H +)(OH2)] forms with stronger electron-donating properties in neutral and basic solutions, and are active catalysts for CO2 hydrogenation in aqueous bicarbonate media at moderate temperature under a total 4-5 MPa (CO2:H2 1:1) pressure. The cobalt complexes containing 4DHBP ligands ([1-OH2]2+ and [1-Cl] +, where 1 = Cp*Co(4DHBP)) display better thermal stability and exhibit notable catalytic activity for CO2 hydrogenation to formate in contrast to the catalytically inactive nonsubstituted bpy analogues [3-OH2]2+ (3 = Cp*Co(bpy)). While the catalyst Cp*Ir(6DHBP)(OH2)2+ in which the pendent oxyanion lowers the barrier for H2 heterolysis via proton transfer through a hydrogen-bonding network involving a water molecule is remarkably effective (ACS Catal. 2013, 3, 856-860), cobalt complexes containing 6DHBP ligands ([2-OH 2]2+ and [2-Cl]+, 2 = Cp*Co(6DHBP)) exhibit lower TOF and TON for CO2 hydrogenation than those with 4DHBP. The low activity is attributed to thermal instability during the hydrogenation of CO2 as corroborated by DFT calculations.

Original languageEnglish
Pages (from-to)12576-12586
Number of pages11
JournalInorganic Chemistry
Volume52
Issue number21
DOIs
Publication statusPublished - Nov 4 2013

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Cobalt
Carbon Dioxide
Hydrogenation
hydrogenation
Protons
carbon dioxide
cobalt
Ligands
catalysts
ligands
Catalysts
formic acid
protons
Proton transfer
thermal instability
Water
X ray crystallography
formates
Bicarbonates
Ultraviolet spectroscopy

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Cp*Co(III) catalysts with proton-responsive ligands for carbon dioxide hydrogenation in aqueous media. / Badiei, Yosra M.; Wang, Wan Hui; Hull, Jonathan F.; Szalda, David J.; Muckerman, James; Himeda, Yuichiro; Fujita, Etsuko.

In: Inorganic Chemistry, Vol. 52, No. 21, 04.11.2013, p. 12576-12586.

Research output: Contribution to journalArticle

Badiei, Yosra M. ; Wang, Wan Hui ; Hull, Jonathan F. ; Szalda, David J. ; Muckerman, James ; Himeda, Yuichiro ; Fujita, Etsuko. / Cp*Co(III) catalysts with proton-responsive ligands for carbon dioxide hydrogenation in aqueous media. In: Inorganic Chemistry. 2013 ; Vol. 52, No. 21. pp. 12576-12586.
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AU - Badiei, Yosra M.

AU - Wang, Wan Hui

AU - Hull, Jonathan F.

AU - Szalda, David J.

AU - Muckerman, James

AU - Himeda, Yuichiro

AU - Fujita, Etsuko

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N2 - New water-soluble pentamethylcyclopentadienyl cobalt(III) complexes with proton-responsive 4,4′- and 6,6′-dihydroxy-2,2′-bipyridine (4DHBP and 6DHBP, respectively) ligands have been prepared and were characterized by X-ray crystallography, UV-vis and NMR spectroscopy, and mass spectrometry. These cobalt(III) complexes with proton-responsive ligands predominantly exist in their deprotonated [Cp*Co(DHBP-2H +)(OH2)] forms with stronger electron-donating properties in neutral and basic solutions, and are active catalysts for CO2 hydrogenation in aqueous bicarbonate media at moderate temperature under a total 4-5 MPa (CO2:H2 1:1) pressure. The cobalt complexes containing 4DHBP ligands ([1-OH2]2+ and [1-Cl] +, where 1 = Cp*Co(4DHBP)) display better thermal stability and exhibit notable catalytic activity for CO2 hydrogenation to formate in contrast to the catalytically inactive nonsubstituted bpy analogues [3-OH2]2+ (3 = Cp*Co(bpy)). While the catalyst Cp*Ir(6DHBP)(OH2)2+ in which the pendent oxyanion lowers the barrier for H2 heterolysis via proton transfer through a hydrogen-bonding network involving a water molecule is remarkably effective (ACS Catal. 2013, 3, 856-860), cobalt complexes containing 6DHBP ligands ([2-OH 2]2+ and [2-Cl]+, 2 = Cp*Co(6DHBP)) exhibit lower TOF and TON for CO2 hydrogenation than those with 4DHBP. The low activity is attributed to thermal instability during the hydrogenation of CO2 as corroborated by DFT calculations.

AB - New water-soluble pentamethylcyclopentadienyl cobalt(III) complexes with proton-responsive 4,4′- and 6,6′-dihydroxy-2,2′-bipyridine (4DHBP and 6DHBP, respectively) ligands have been prepared and were characterized by X-ray crystallography, UV-vis and NMR spectroscopy, and mass spectrometry. These cobalt(III) complexes with proton-responsive ligands predominantly exist in their deprotonated [Cp*Co(DHBP-2H +)(OH2)] forms with stronger electron-donating properties in neutral and basic solutions, and are active catalysts for CO2 hydrogenation in aqueous bicarbonate media at moderate temperature under a total 4-5 MPa (CO2:H2 1:1) pressure. The cobalt complexes containing 4DHBP ligands ([1-OH2]2+ and [1-Cl] +, where 1 = Cp*Co(4DHBP)) display better thermal stability and exhibit notable catalytic activity for CO2 hydrogenation to formate in contrast to the catalytically inactive nonsubstituted bpy analogues [3-OH2]2+ (3 = Cp*Co(bpy)). While the catalyst Cp*Ir(6DHBP)(OH2)2+ in which the pendent oxyanion lowers the barrier for H2 heterolysis via proton transfer through a hydrogen-bonding network involving a water molecule is remarkably effective (ACS Catal. 2013, 3, 856-860), cobalt complexes containing 6DHBP ligands ([2-OH 2]2+ and [2-Cl]+, 2 = Cp*Co(6DHBP)) exhibit lower TOF and TON for CO2 hydrogenation than those with 4DHBP. The low activity is attributed to thermal instability during the hydrogenation of CO2 as corroborated by DFT calculations.

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