A synthetic model for the oxygen-evolving complex in Sr<sup>2+</sup>-containing photosystem II

Chen, Changhui; Zhang, Chunxi; Dong, Hongbiao; Zhao, Jingquan

doi:10.1039/c4cc02349h

Cited by 30 publications

(20 citation statements)

References 46 publications

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“…In 2014, we reported a heterometallic cluster containing two Mn IV 3SrO4-clusters linked by one 2-oxide bridge [113], which mimics the three types of oxide bridges (2-oxide, 3-oxide, and 4-oxide) and the Mn3SrO4 cubane of the Sr 2+ -containing OEC [30] at the same time (Figure 8). In 2014, we reported a heterometallic cluster containing two Mn IV 3 SrO 4 -clusters linked by one µ 2 -oxide bridge [113], which mimics the three types of oxide bridges (µ 2 -oxide, µ 3 -oxide, and µ 4 -oxide) and the Mn 3 SrO 4 cubane of the Sr 2+ -containing OEC [30] at the same time (Figure 8). It should be pointed out that, even though all complexes shown in Figures 7 and 8 have mimicked some key structural motifs of the Mn3CaO4 or Mn3SrO4 cubane in the OEC, until recently, it remains a great challenge to synthesize the entire Mn4Ca-cluster with similar ligands, as seen in the OEC of PSII.…”

Section: Challenge For the Synthesis Of The Oec In The Laboratorymentioning

confidence: 94%

Mimicking the Catalytic Center for the Water-Splitting Reaction in Photosystem II

Yao

Chen

et al. 2020

Catalysts

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The oxygen-evolving center (OEC) in photosystem II (PSII) of plants, algae and cyanobacteria is a unique natural catalyst that splits water into electrons, protons and dioxygen. The crystallographic studies of PSII have revealed that the OEC is an asymmetric Mn4CaO5-cluster. The understanding of the structure-function relationship of this natural Mn4CaO5-cluster is impeded mainly due to the complexity of the protein environment and lack of a rational chemical model as a reference. Although it has been a great challenge for chemists to synthesize the OEC in the laboratory, significant advances have been achieved recently. Different artificial complexes have been reported, especially a series of artificial Mn4CaO4-clusters that closely mimic both the geometric and electronic structures of the OEC in PSII, which provides a structurally well-defined chemical model to investigate the structure-function relationship of the natural Mn4CaO5-cluster. The deep investigations on this artificial Mn4CaO4-cluster could provide new insights into the mechanism of the water-splitting reaction in natural photosynthesis and may help the development of efficient catalysts for the water-splitting reaction in artificial photosynthesis.

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Section: Challenge For the Synthesis Of The Oec In The Laboratorymentioning

confidence: 94%

Mimicking the Catalytic Center for the Water-Splitting Reaction in Photosystem II

Yao

Chen

et al. 2020

Catalysts

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“…(3) Ca离子如何发挥作用 [39] ? (4) 哪些水分子是底物水分子 [59] [76] 、难以在高价Mn簇中引入生物配体 [55] 的合成难题. 最近, 受生物OEC组装规律的启示 [77] , 本课题组 [70,78] 借助高活性的单核Mn 3+ 化合物与Mn3CaO4立方烷原位加成反应, 成功合成出不对称的Mn4Ca-簇合物…”

Section: 例如unclassified

From natural photosynthesis to artificial photosynthesis

Zhang¹

2016

Sci. Sin.-Chim

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“…In the OEC, Ca 2+ acts as an essential cofactor in the manganese–calcium–oxygen cluster (Mn 4 CaO 5 ), which is responsible for water oxidation in PS II 24–30. Among redox‐inactive metal ions, Sr 2+ is the only surrogate that can restore the activity of OEC after Ca 2+ removal 31–35. The similar size and Lewis acidity of the Ca 2+ and Sr 2+ ions may be responsible for their ability to function in OEC.…”

Section: Introductionmentioning

confidence: 99%

Lewis Acid Coupled Electron Transfer of Metal–Oxygen Intermediates

Fukuzumi

Ohkubo

Lee

et al. 2015

Chemistry A European J

136

121

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Redox-inactive metal ions and Brønsted acids that function as Lewis acids play pivotal roles in modulating the redox reactivity of metal-oxygen intermediates, such as metal-oxo and metal-peroxo complexes. The mechanisms of the oxidative CH bond cleavage of toluene derivatives, sulfoxidation of thioanisole derivatives, and epoxidation of styrene derivatives by mononuclear nonheme iron(IV)-oxo complexes in the presence of triflic acid (HOTf) and Sc(OTf)3 have been unified as rate-determining electron transfer coupled with binding of Lewis acids (HOTf and Sc(OTf)3 ) by iron(III)-oxo complexes. All logarithms of the observed second-order rate constants of Lewis acid-promoted oxidative CH bond cleavage, sulfoxidation, and epoxidation reactions of iron(IV)-oxo complexes exhibit remarkably unified correlations with the driving forces of proton-coupled electron transfer (PCET) and metal ion-coupled electron transfer (MCET) in light of the Marcus theory of electron transfer when the differences in the formation constants of precursor complexes were taken into account. The binding of HOTf and Sc(OTf)3 to the metal-oxo moiety has been confirmed for Mn(IV) -oxo complexes. The enhancement of the electron-transfer reactivity of metal-oxo complexes by binding of Lewis acids increases with increasing the Lewis acidity of redox-inactive metal ions. Metal ions can also bind to mononuclear nonheme iron(III)-peroxo complexes, resulting in acceleration of the electron-transfer reduction but deceleration of the electron-transfer oxidation. Such a control on the reactivity of metal-oxygen intermediates by binding of Lewis acids provides valuable insight into the role of Ca(2+) in the oxidation of water to dioxygen by the oxygen-evolving complex in photosystem II.

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A synthetic model for the oxygen-evolving complex in Sr²⁺-containing photosystem II

Abstract: A novel heterometallic MnSr complex containing the Mn3SrO4 cuboidal moiety and all types of μ-O(2-) moieties observed in the oxygen-evolving complex (OEC) in Sr(2+)-containing photosystem II (PSII) has been synthesized and characterized, which provides a new synthetic model of the OEC.

Cited by 30 publications

References 46 publications

Mimicking the Catalytic Center for the Water-Splitting Reaction in Photosystem II

Mimicking the Catalytic Center for the Water-Splitting Reaction in Photosystem II

From natural photosynthesis to artificial photosynthesis

Lewis Acid Coupled Electron Transfer of Metal–Oxygen Intermediates

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A synthetic model for the oxygen-evolving complex in Sr2+-containing photosystem II

Abstract: A novel heterometallic MnSr complex containing the Mn3SrO4 cuboidal moiety and all types of μ-O(2-) moieties observed in the oxygen-evolving complex (OEC) in Sr(2+)-containing photosystem II (PSII) has been synthesized and characterized, which provides a new synthetic model of the OEC.

Cited by 30 publications

References 46 publications

Mimicking the Catalytic Center for the Water-Splitting Reaction in Photosystem II

Mimicking the Catalytic Center for the Water-Splitting Reaction in Photosystem II

From natural photosynthesis to artificial photosynthesis

Lewis Acid Coupled Electron Transfer of Metal–Oxygen Intermediates

Contact Info

Product

Resources

About

A synthetic model for the oxygen-evolving complex in Sr²⁺-containing photosystem II