Closer to Photosystem II: A Co<sub>4</sub>O<sub>4</sub> Cubane Catalyst with Flexible Ligand Architecture

Evangelisti, Fabio; Güttinger, Robin; Moré, René; Luber, Sandra; Patzke, Greta R.

doi:10.1021/ja4098302

Cited by 156 publications

(132 citation statements)

References 40 publications

(83 reference statements)

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“…Remarkable mechanistic insight into the O–O bond formation reaction has been obtained from studies of Mn (refs 38,39,46 ) and Co (refs 47–50 ) tetrametallic cubane model complexes. Up to now these cubane OEC models generally support the oxo/oxyl radical coupling mechanism to form the O–O bond.…”

Section: Discussionmentioning

confidence: 99%

Evidence for an oxygen evolving iron–oxo–cerium intermediate in iron-catalysed water oxidation

et al. 2015

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The non-haem iron complex α-[FeII(CF3SO3)2(mcp)] (mcp = (N,N′-dimethyl-N,N′-bis(2-pyridylmethyl)-1,2-cis-diaminocyclohexane) reacts with CeIV to oxidize water to O2, representing an iron-based functional model for the oxygen evolving complex of photosystem II. Here we trap an intermediate, characterized by cryospray ionization high resolution mass spectrometry and resonance Raman spectroscopy, and formulated as [(mcp)FeIV(O) (μ-O)CeIV(NO3)3]+, the first example of a well-characterized inner-sphere complex to be formed in cerium(IV)-mediated water oxidation. The identification of this reactive FeIV–O–CeIV adduct may open new pathways to validate mechanistic notions of an analogous MnV–O–CaII unit in the oxygen evolving complex that is responsible for carrying out the key O–O bond forming step.

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Section: Discussionmentioning

confidence: 99%

Evidence for an oxygen evolving iron–oxo–cerium intermediate in iron-catalysed water oxidation

et al. 2015

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“…42 Finally, we did not consider dimerization of cobalt-oxyl species, as was described for a ruthenium catalyst, 40 due to steric hindrance by the ligands and the absence of experimental evidence for second order kinetics with regard to [1]. 36,42 Energy profiles.…”

Section: Scheme 2 Oxo-oxo Coupling Pathwaymentioning

confidence: 99%

What Influences the Water Oxidation Activity of a Bioinspired Molecular Co^II₄O₄ Cubane? An In-Depth Exploration of Catalytic Pathways

Hodel

Luber

2016

ACS Catal.

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Solar light to chemical energy conversion is an important topic of research due to global climate change and an increasing shortage of fossil fuels. Artificial photosynthesis, as a possible solution to these issues, is strongly dependent on efficient water oxidation. The exact way in which molecular water oxidation catalysts (WOCs), in particular biomimetic cubanes, perform the task of splitting water into oxygen, protons, and electrons still remains unclear to a large extent. We investigated the reaction mechanism of the recently presented first Co(II)-based WOC, [CoII4(hmp)4( -OAc)2( 2-OAc)2(H2O)2] (hmp = 2-(hydroxymethyl)pyridine) [Evangelisti, F.; Güttinger, R.; Moré, R.; Luber, S.; Patzke, G. R. J. Am. Chem. Soc. 2013, 135, 18734−18737], which is one of the rare stable homogeneous cubane-type WOCs and the design of which has been inspired by nature's oxygen evolving complex of photosystem II (PSII). Two possible different catalytic cycles have been envisioned: A single-site pathway involving one cobalt center and a water attack on an oxo ligand or, alternatively, an oxo-oxo coupling pathway where, after the replacement of an acetate ligand by water, two terminal oxo ligands of the cubane couple and are released as O2. Using density functional theory and an explicit solvation shell, we compare relative free energies of all states of the catalytic pathways, also with different ligand environments, and analyze the stability and reactivity of each catalytic state in detail. Furthermore, we compute barriers and reaction paths for water attack and O2 release steps. With this knowledge at hand, we propose possibilities to tune catalytic activity paving the way to informed design of high-performance PSII mimics.

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“…[1][2][3][4][5][6][7][8][9][10][11]. Ligand design has became a major concept in these investigations to tailor the stability and chemical properties of the complex [12].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, structures, and catalytic studies of new copper(II) complexes with arene-linked pyrazolyl methane ligands

Wang

Hou

et al. 2015

Journal of Coordination Chemistry

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L1 = 1,4-bis((1H-pyrazol-1-yl)methyl)benzene; L2 = 1,4-bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)benzene; H 2 dipic = 2,6-pyridinedicarboxylic acid), were synthesized by reaction of copper salt, arene-linked pyrazolyl methane ligands and 2,6-pyridinedicarboxylic acid in 95% C 2 H 5 OH. They were characterized by elemental analysis, IR, UV-Vis, single crystal X-ray diffraction analysis, X-ray powder diffraction and thermogravimetric analysis. We explored the application of the copper complexes in bromination reactions; the complexes exhibited bromination catalytic activity in single-pot reaction for conversion of phenol red into bromophenol blue. A feasible bromination reaction mechanism of copper complexes was proposed.

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Closer to Photosystem II: A Co₄O₄ Cubane Catalyst with Flexible Ligand Architecture

Cited by 156 publications

References 40 publications

Evidence for an oxygen evolving iron–oxo–cerium intermediate in iron-catalysed water oxidation

Evidence for an oxygen evolving iron–oxo–cerium intermediate in iron-catalysed water oxidation

What Influences the Water Oxidation Activity of a Bioinspired Molecular Co^II₄O₄ Cubane? An In-Depth Exploration of Catalytic Pathways

Synthesis, structures, and catalytic studies of new copper(II) complexes with arene-linked pyrazolyl methane ligands

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Closer to Photosystem II: A Co4O4 Cubane Catalyst with Flexible Ligand Architecture

Cited by 156 publications

References 40 publications

Evidence for an oxygen evolving iron–oxo–cerium intermediate in iron-catalysed water oxidation

Evidence for an oxygen evolving iron–oxo–cerium intermediate in iron-catalysed water oxidation

What Influences the Water Oxidation Activity of a Bioinspired Molecular CoII4O4 Cubane? An In-Depth Exploration of Catalytic Pathways

Synthesis, structures, and catalytic studies of new copper(II) complexes with arene-linked pyrazolyl methane ligands

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Closer to Photosystem II: A Co₄O₄ Cubane Catalyst with Flexible Ligand Architecture

What Influences the Water Oxidation Activity of a Bioinspired Molecular Co^II₄O₄ Cubane? An In-Depth Exploration of Catalytic Pathways