Preparation and Characterization of Different Two Types of Di-<i>μ</i>-oxo Dimanganese(IV) Complexes with Tetradentate Schiff Bases

Torayama, Hitoshi; Nishide, Tamao; Asada, Hideyuki; Fujiwara, Manabu; Matsushita, Takayuki

doi:10.1246/cl.1996.387

Cited by 12 publications

(3 citation statements)

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“…This is to be expected from the crystal structure given that since the distance between the Mn 3+ ions is quite large (3.235 Å). Additionally, the absence of any long‐range antiferromagnetic ordering is consistent with the small magnitudes of the exchange constants between the magnetic ions, as noted above [68–70] …”

Section: Resultssupporting

confidence: 65%

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Search for Structurally Resembled Mn/Ca Cubane Core of the Oxygen Evolving Complex of Photosystem II Yielded Mn^IV, Mn^III₃Mn^II and Mn^III₂Ca^II₂Entities: Structure and Magnetism

et al. 2022

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The aim of the paper was to synthesize Mn/Ca entities that are structurally similar to the reported oxygen‐evolving complex (OEC) of photosystem II (PSII). Here we have ventured Schiff base combinations of racemic (±)‐3‐Aminopropane‐1,2‐diol and Salicyladehyde (H3L1)/o‐Vanillin (H3L2) with varied ratios of ligand : CaIIsalt : MnIIIsalt. Interestingly, H3L2 : CaCl2 : MnCl2 (2 : 1 : 1) afforded [{MnIII2CaII2(HL2)2Cl2(μ3‐OH)2(H2O)6}Cl2 ⋅ 2H2O] (3) whereas H3L1 : CaCl2 : Mn(acetate)2 (2 : 1 : 1) and H3L1 : CaCl2 : MnCl2 (2 : 1 : 2), generated [{MnIV(HL1)2}2 ⋅ 6H2O](1) and [{MnIII3MnII(HL1)3(μ2‐Cl)3(μ3‐O)} ⋅ 2CH3OH ⋅ 2H2O] (2) respectively. More importantly, we have been able to get a structure which offers partial similarity to reported structure of the OEC. Variable temperature magnetic susceptibility measurements have been performed in the 1.8–30 K region for all the compounds. Overall, these studies provide a critical understanding for the rational design and construction of synthetic OEC.

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Section: Resultssupporting

confidence: 65%

“…Additionally, the absence of any long-range antiferromagnetic ordering is consistent with the small magnitudes of the exchange constants between the magnetic ions, as noted above. [68][69][70]…”

Section: Magnetic Propertiesmentioning

confidence: 99%

Search for Structurally Resembled Mn/Ca Cubane Core of the Oxygen Evolving Complex of Photosystem II Yielded Mn^IV, Mn^III₃Mn^II and Mn^III₂Ca^II₂Entities: Structure and Magnetism

et al. 2022

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“…Complex 15 has been very recently reported as the unexpected result from the reaction of salophenH 2 and KMnO 4 . An analogous structure appeared on a substituted salen made from some Mn(III) oxidation .…”

Section: Resultsmentioning

confidence: 82%

Carbon−Carbon Bonds Functioning as Electron Shuttles: The Generation of Electron-Rich Manganese(II)−Schiff Base Complexes and Their Redox Chemistry

Gallo

Solari

et al. 1997

J. Am. Chem. Soc.

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The reduction of [Mn(II)-salophen] derivatives [salophen ) N,N ′-ethylenebis(salicylideneaminato) dianion] led to the formation of C-C bridged dimers. Such C-C bonds function as two electron shuttles in electron-transfer reactions. The reduction of [Mn(salophen)(THF)] 2 (1) and [Mn(3,5-Bu t 4 salophen)(THF)] 2 (3) with 2 equiv of sodium metal led to the corresponding single C-C bond bridged dimers, [Mn 2 (salophen 2 )Na 2 (DME) 4 ] (5) [salophen 2 ) C-C bonded salophen dimer] and [Mn 2 (3,5-Bu t 4 salophen 2 )Na 2 (DME) 6 ] (7), respectively. Complexes 5 and 7 undergo a further two electron reduction to [Mn 2 (*salophen 2 *)Na 4 (DME) 6 ] (6) [*salophen 2 * ) C-C doubly bonded salophen dimer] and [Mn 2 (*3,5-Bu t 4 salophen 2 *)Na 4 (DME) 4 ] (8), respectively, both containing a double C-C bridge. The obtention of [Mn 2 {salophen(Me)CH 2 )} 2 Na 4 (DME) 4 ] (9) from [Mn(salophen-Me 2 )(THF)] 2 (2) strongly supports the existence of free radical precursors in the formation of C-C bonds. Complex 6 has been used as a source of four electrons in a number of reactions, thus reduction of Ag + , PhCH 2 Cl, p-benzoquinone, and [Co II (MeOsalen)] occurs with the regeneration of the starting material 1. The C-C bond cleavage is the source of electrons, without being involved in any reaction as a reactive site. With stronger oxidizing agents not only complexes 6 and 8 transfer the electrons stored at the C-C bonds but also the metal undergoes a change in the oxidation state. The reaction of 6 with dioxygen produces a novel form of di-µ-oxo-Mn(IV) dimers, where the salophen ligand displays a bridging bonding mode in [Mn 2 (µ-salophen) 2 (µ-O) 2 ] (15) and [Mn 2 (µ-3,5-Bu t salophen) 2 (µ-O) 2 ] (16).

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High-valent bis(oxo)-bridged dinuclear manganese oxamates: Synthesis, crystal structures, magnetic properties, and electronic structure calculations of bis(μ-oxo)dimanganese(IV) complexes with a binucleating o-phenylenedioxamate ligand

Ruiz-Garcı́a¹,

Pardo²,

Muñoz³

et al. 2007

Inorganica Chimica Acta

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Preparation and Characterization of Different Two Types of Di-μ-oxo Dimanganese(IV) Complexes with Tetradentate Schiff Bases

Cited by 12 publications

References 5 publications

Search for Structurally Resembled Mn/Ca Cubane Core of the Oxygen Evolving Complex of Photosystem II Yielded Mn^IV, Mn^III₃Mn^II and Mn^III₂Ca^II₂Entities: Structure and Magnetism

Search for Structurally Resembled Mn/Ca Cubane Core of the Oxygen Evolving Complex of Photosystem II Yielded Mn^IV, Mn^III₃Mn^II and Mn^III₂Ca^II₂Entities: Structure and Magnetism

Carbon−Carbon Bonds Functioning as Electron Shuttles: The Generation of Electron-Rich Manganese(II)−Schiff Base Complexes and Their Redox Chemistry

High-valent bis(oxo)-bridged dinuclear manganese oxamates: Synthesis, crystal structures, magnetic properties, and electronic structure calculations of bis(μ-oxo)dimanganese(IV) complexes with a binucleating o-phenylenedioxamate ligand

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Preparation and Characterization of Different Two Types of Di-μ-oxo Dimanganese(IV) Complexes with Tetradentate Schiff Bases

Cited by 12 publications

References 5 publications

Search for Structurally Resembled Mn/Ca Cubane Core of the Oxygen Evolving Complex of Photosystem II Yielded MnIV, MnIII3MnII and MnIII2CaII2Entities: Structure and Magnetism

Search for Structurally Resembled Mn/Ca Cubane Core of the Oxygen Evolving Complex of Photosystem II Yielded MnIV, MnIII3MnII and MnIII2CaII2Entities: Structure and Magnetism

Carbon−Carbon Bonds Functioning as Electron Shuttles: The Generation of Electron-Rich Manganese(II)−Schiff Base Complexes and Their Redox Chemistry

High-valent bis(oxo)-bridged dinuclear manganese oxamates: Synthesis, crystal structures, magnetic properties, and electronic structure calculations of bis(μ-oxo)dimanganese(IV) complexes with a binucleating o-phenylenedioxamate ligand

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Search for Structurally Resembled Mn/Ca Cubane Core of the Oxygen Evolving Complex of Photosystem II Yielded Mn^IV, Mn^III₃Mn^II and Mn^III₂Ca^II₂Entities: Structure and Magnetism

Search for Structurally Resembled Mn/Ca Cubane Core of the Oxygen Evolving Complex of Photosystem II Yielded Mn^IV, Mn^III₃Mn^II and Mn^III₂Ca^II₂Entities: Structure and Magnetism