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| 2. |
- Arafa, Wael A. A., et al.
(författare)
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Dinuclear manganese complexes for water oxidation : evaluation of electronic effects and catalytic activity
- 2014
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 16:24, s. 11950-11964
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Tidskriftsartikel (refereegranskat)abstract
- During recent years significant progress has been made towards the realization of a sustainable and carbon-neutral energy economy. One promising approach is photochemical splitting of H2O into O-2 and solar fuels, such as H-2. However, the bottleneck in such artificial photosynthetic schemes is the H2O oxidation half reaction where more efficient catalysts are required that lower the kinetic barrier for this process. In particular catalysts based on earth-abundant metals are highly attractive compared to catalysts comprised of noble metals. We have now synthesized a library of dinuclear Mn-2 (II,III) catalysts for H2O oxidation and studied how the incorporation of different substituents affected the electronics and catalytic efficiency. It was found that the incorporation of a distal carboxyl group into the ligand scaffold resulted in a catalyst with increased catalytic activity, most likely because of the fact that the distal group is able to promote proton-coupled electron transfer (PCET) from the high-valent Mn species, thus facilitating O-O bond formation.
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| 3. |
- Das, Biswanath, et al.
(författare)
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Water oxidation catalyzed by molecular di- and nonanuclear Fe complexes: importance of a proper ligand framework
- 2016
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Ingår i: Dalton Transactions. - : ROYAL SOC CHEMISTRY. - 1477-9226 .- 1477-9234. ; 45:34, s. 13289-13293
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Tidskriftsartikel (refereegranskat)abstract
- The synthesis of two molecular iron complexes, a dinuclear iron(III,III) complex and a nonanuclear iron complex, based on the di-nucleating ligand 2,2-(2-hydroxy-5-methyl-1,3-phenylene)bis(1H-benzo[d]imidazole-4-carboxylic acid) is described. The two iron complexes were found to drive the oxidation of water by the one-electron oxidant [Ru(bpy)(3)](3+).
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| 4. |
- Gao, Weiming, et al.
(författare)
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Attachment of a Hydrogen-Bonding Carboxylate Side Chain to an FeFe -Hydrogenase Model Complex : Influence on the Catalytic Mechanism
- 2010
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Ingår i: Chemistry - A European Journal. - Weinheim : Wiley. - 0947-6539 .- 1521-3765. ; 16:8, s. 2537-2546
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Tidskriftsartikel (refereegranskat)abstract
- Azapropanedithiolate (adt)-bridged model complexes of [FeFe]-hydrogenase bearing a carboxylic acid functionality have been designed with the aim of decreasing the potential for reduction of protons to hydrogen. Protonation of the bisphosphine complexes 4-6 has been studied by in situ IR and NMR spectroscopy, which revealed that protonation with triflic acid most likely takes place first at the N-bridge for complex 4 but at the Fe Fe bond for complexes 5 and 6. Using an excess of acid, the diprotonated species could also be observed, but none of the protonated species was sufficiently stable to be isolated in a pure state. Electrochemical studies have provided an insight into the catalytic mechanisms under strongly acidic conditions, and have also shown that complexes 3 and 6 are electro-active in aqueous solution even in the absence of acid, presumably due to hydrogen bonding. Hydrogen evolution, driven by visible light, has been observed for three-component systems consisting of [Ru(bpy)(3)](2+), complex 1, 2, or 3, and ascorbic acid in CH3CN/D2O solution by on-line mass spectrometry.
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| 5. |
- Gao, Yan, et al.
(författare)
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Nucleophilic Attack of Hydroxide on a Mn-V Oxo Complex : A Model of the O-O Bond Formation in the Oxygen Evolving Complex of Photosystem II
- 2009
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 131:25, s. 8726-
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Tidskriftsartikel (refereegranskat)abstract
- A manganese(III) corrole complex, 1, has been synthesized and used to study a potential mechanism for oxidation of water to molecular oxygen. Oxidation by t-BuOOH gave the Mn-V=O complex 2. Addition of hydroxide Led to release of oxygen via the Mn-IV complex 4 and regeneration of complex 1. It could be shown that the oxygen from O-18-labeted water was incorporated in both the formed molecular oxygen and the peroxy intermediate 4.
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| 6. |
- Huang, Yong, et al.
(författare)
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An Air-Stable Fe3S4 Complex with Properties Similar to Those of the HOXair State of the Diiron Hydrogenases
- 2012
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Ingår i: European Journal of Inorganic Chemistry. - : Wiley. - 1434-1948 .- 1099-1948 .- 1099-0682. ; :27, s. 4259-4263
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Tidskriftsartikel (refereegranskat)abstract
- A Fe3S4 complex bridged by azapropanedithiolate (adt), complex 6, was prepared as a potential model of the HOXair state of [FeFe]-hydrogenases. Complex 6 was characterized by IR and 1H NMR spectroscopy, and its structure was determined by X-ray crystallography. The electrochemical studies show that complex 6 is redox-active under acidic conditions, which provides insight into the catalytic mechanism. Hydrogen evolution, driven by visible light, was observed in CH3CN/D2O solution by online mass spectroscopy.
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| 9. |
- Karlsson, Erik A., et al.
(författare)
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Synthesis and Electron-Transfer Processes in a New Family of Ligands for Coupled Ru-Mn2 Complexes
- 2014
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Ingår i: ChemPlusChem. - : Wiley. - 2192-6506. ; 79:7, s. 936-950
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Tidskriftsartikel (refereegranskat)abstract
- A series of [Ru(bpy)(3)](2+)-type (bpy= 2,2'-bipyridine) photosensitisers have been coupled to a ligand for Mn, which is expected to give a dinuclear complex that is active as a water oxidation catalyst. Unexpectedly, photophysical studies showed that the assemblies had very short lived excited states and that the decay patterns were complex and strongly dependent on pH. One dyad was prepared that was capable of catalysing chemical water oxidation by using [Ru(bpy)(3)](3+) as an oxidant. However, photochemical water oxidation in the presence of an external electron acceptor failed, presumably because the short excited-state lifetime precluded initial electron transfer to the added acceptor. The photophysical behaviour could be explained by the presence of an intricate excited-state manifold, as also suggested by time-dependent DFT calculations.
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