Cleavage of sulfur dioxide on (.eta.5-C5Me5)2Mo2(.mu.-S2)(.mu.-S)2 to form S8 and a thiosulfate complex (.eta.5-C5Me5)2Mo2(.mu.-S2)(.mu.-S)(.mu.-SSO3). Possible role in homogeneous hydrogenation of sulfur dioxide catalyzed by molybdenum-sulfur complexes

Kubas, Gregory J.; Ryan, R. R.; Kubat-Martin, Kimberly A.

doi:10.1021/ja00202a024

Cited by 46 publications

(16 citation statements)

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“…[25] can exist as three different isomeric structures (see Scheme 2), and experimental [17] and computational [18] studies have shown that the interconversions between them can be thermally [19] or photochemically [17] promoted. Fortunately, although 1-b is the most stable isomer, [20] the synthetic method of Wachter et al under mild reaction conditions allows the isolation of 1-a, [19,21] the reactivity of which has proven especially remarkable. Indeed, if H 2 (1 atm) is added to a CH 2 Cl 2 solution of 1-a, the formation of [Cp*Mo] 2 (μ-S) 2 (μ-SH) 2 (2) is quantitative within 90 min in a process that involves the cleavage of the S-S bond of the μ-S 2 moiety in 1-a.…”

Section: Introductionmentioning

confidence: 99%

Computational Insights into the Mechanisms of H₂ Activation and H₂/D₂ Isotope Exchange by Dimolybdenum Tetrasulfide Complexes

Algarra

2016

Eur J Inorg Chem

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The mechanisms for H 2 activation by [Cp*Mo] 2 (μ-S) 2 (μ-S 2) (1-a, Cp* = pentamethylcyclopentadienyl) and its reaction product [Cp*Mo] 2 (μ-S) 2 (μ-SH) 2 (2) have been investigated by DFT methods. The reaction of 1-a involves the homolytic addition of H 2 to its μ-S ligands, followed by the cleavage of the S-S bond of the μ-S 2 ligand in a subsequent step. Complex 2 can adopt five conformations that only differ in the stereochemistry of the μ-SH and μ-S ligands; although an isomer with adjacent μ-S ligands (2-a) is formed initially, it then isomerises

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Section: Introductionmentioning

confidence: 99%

Computational Insights into the Mechanisms of H₂ Activation and H₂/D₂ Isotope Exchange by Dimolybdenum Tetrasulfide Complexes

Algarra

2016

Eur J Inorg Chem

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“…Among 83 structures with thiosulfate ligands deposited in CSD, fifteen contain S 2 O 3 2– as a S‐bridge 11. Some of the thiosulfate complexes feature planar or folded M 2 (μ‐S) 2 ring ( M = Cd,12 Fe,13 or Mo14) but till now dinuclear Ni II thiosulfate complexes with Ni 2 (μ‐S) 2 motif are unknown. There are some nickel thiosulfates, however in most cases they are mononuclear with S 2 O 3 2– as a monodentate ligand,14 chelating one15c,16 or as a counterion [15b–d, 17] .…”

Section: Resultsmentioning

confidence: 99%

The First Dinuclear Nickel(II) Thiosulfate Obtained From Oxidation of Tri‐tert‐butoxysilanethiol. Contributions to the Chemistry of Silicon‐Sulfur Compounds No. 78^[1]

Pladzyk

Daca

Ponikiewski

2012

Zeitschrift anorg allge chemie

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The title complex, neutral {[Ni 2 (μ-S 2 O 3 ) 2 (C 7 H 9 N) 4 -H 2 O]C 7 H 8 } (1), presents a dinuclear structure with the thiosulfate group acting as a (S,O) chelate and simultaneously as a (S) bridge. The molecular structure was determined by X-ray crystallography. Complex 1 crystallizes as a hydrogen-bonded dimer with molecule of toluene solvent in the unit cell. The environment of both central nickel * Dr. A. Pladzyk

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“…In wet reduction, SO 2 is absorbed in the liquid phase and then reduced to elemental sulfur. The common reduction process includes the photochemical reduction of SO 2 by magnesium tetraphenylporphyrin, , catalytic reduction of SO 2 using Cp* 2 Mo 2 S 4 as the catalyst and hydrogen as the reductant, electrochemical reduction of SO 2 in dimethylformamide (DMF), and Bio-FGD . Considering that CO is one of the waste gases generated from coal-fired power plants, wet reduction of SO 2 by CO seems to be an alternative technology in terms of economy.…”

Section: Introductionmentioning

confidence: 99%

Selenium-Assisted Reduction of Sulfur Dioxide by Carbon Monoxide in the Liquid Phase

Yang

Chai

Zhu

et al. 2017

Ind. Eng. Chem. Res.

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Regenerable flue gas desulfurization (FGD) is highly attractive because of the transformation of sulfur dioxide (SO2) to high-value products. In this study, selenium-assisted SO2 reduction by carbon monoxide (CO) in the liquid phase [dimethylformamide (DMF) + water (H2O) mixture] is proposed and applied in the FGD process. This process realizes recycle of the elemental sulfur product under room temperature. Moreover, results show that both the selenium catalyst and DMF solvent have good stability and can be well recycled, implying that this process is economically feasible. Furthermore, the mechanism of selenium-assisted SO2 reduction by CO in DMF/H2O is investigated. Results show that the selenium catalyst dissolves in solution and forms Se n 2– species, which are the active intermediates and promote formation of the sulfur product.

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Cleavage of sulfur dioxide on (.eta.5-C5Me5)2Mo2(.mu.-S2)(.mu.-S)2 to form S8 and a thiosulfate complex (.eta.5-C5Me5)2Mo2(.mu.-S2)(.mu.-S)(.mu.-SSO3). Possible role in homogeneous hydrogenation of sulfur dioxide catalyzed by molybdenum-sulfur complexes

Cited by 46 publications

References 3 publications

Computational Insights into the Mechanisms of H₂ Activation and H₂/D₂ Isotope Exchange by Dimolybdenum Tetrasulfide Complexes

Computational Insights into the Mechanisms of H₂ Activation and H₂/D₂ Isotope Exchange by Dimolybdenum Tetrasulfide Complexes

The First Dinuclear Nickel(II) Thiosulfate Obtained From Oxidation of Tri‐tert‐butoxysilanethiol. Contributions to the Chemistry of Silicon‐Sulfur Compounds No. 78^[1]

Selenium-Assisted Reduction of Sulfur Dioxide by Carbon Monoxide in the Liquid Phase

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Cleavage of sulfur dioxide on (.eta.5-C5Me5)2Mo2(.mu.-S2)(.mu.-S)2 to form S8 and a thiosulfate complex (.eta.5-C5Me5)2Mo2(.mu.-S2)(.mu.-S)(.mu.-SSO3). Possible role in homogeneous hydrogenation of sulfur dioxide catalyzed by molybdenum-sulfur complexes

Cited by 46 publications

References 3 publications

Computational Insights into the Mechanisms of H2 Activation and H2/D2 Isotope Exchange by Dimolybdenum Tetrasulfide Complexes

Computational Insights into the Mechanisms of H2 Activation and H2/D2 Isotope Exchange by Dimolybdenum Tetrasulfide Complexes

The First Dinuclear Nickel(II) Thiosulfate Obtained From Oxidation of Tri‐tert‐butoxysilanethiol. Contributions to the Chemistry of Silicon‐Sulfur Compounds No. 78[1]

Selenium-Assisted Reduction of Sulfur Dioxide by Carbon Monoxide in the Liquid Phase

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Computational Insights into the Mechanisms of H₂ Activation and H₂/D₂ Isotope Exchange by Dimolybdenum Tetrasulfide Complexes

Computational Insights into the Mechanisms of H₂ Activation and H₂/D₂ Isotope Exchange by Dimolybdenum Tetrasulfide Complexes

The First Dinuclear Nickel(II) Thiosulfate Obtained From Oxidation of Tri‐tert‐butoxysilanethiol. Contributions to the Chemistry of Silicon‐Sulfur Compounds No. 78^[1]