Oxidation at a Dimolybdenum(V) Sulfur Bridge. Formation of SO and SO<sub>2</sub> Bridges. Facile Extrusion of SO from the SO<sub>2</sub> Bridge

Wang, Runtong; Mashuta, Mark S.; Richardson, John F.; Noble, Mark E.

doi:10.1021/ic951518k

Cited by 22 publications

(29 citation statements)

References 68 publications

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“…We also found WS 4 2Ϫ ,despite its reported greater redox stability, to react with Cu II identically to TTM in its reaction stoichiometry, redox changes and oxygenation. Recently, Noble et al [30] have shown that S coordinated at a dimolybdenum centre can undergo conversion into coordinated SO (sulfoxide) and coordinated SO 2 (sulfone).…”

Section: Redox Activitymentioning

confidence: 99%

Thiomolybdates — Simple but Very Versatile Reagents

Laurie

2000

Eur. J. Inorg. Chem.

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A large number of thiometallate anions, MOxS4−xn−, and some of the seleno analogues, are known in which M is a transition metal in a high oxidation state. They are characterised by their strong colours arising from low energy S(Se)→M charge transfer transitions, by unusual redox properties and by their ability to act as ligands to produce a wide range of heterometal complexes. This review outlines some of these properties associated with the thiometallate anions of molybdenum(VI). These anions are prepared by passing H2S through an alkaline molybdate solution, giving a sequential replacement of O atoms by S and ultimately MoS42− (TTM) as product. The thiomolybdates, particularly TTM, have been the most intensively studied because of their ease of preparation, their relatively greater thermal and hydrolytic stabilities and their biological roles. Unusual redox changes which involve internal electron transfer have been shown by reaction with organic disulfides and with CuII. In the latter case insoluble polymeric products are readily formed which, from EPR and EXAFS studies, involve S‐bridged reduced Cu and Mo centres. Reaction of TTM with CuI, on the other hand, produces a range of complexes in which from 1 to 6 Cu ions add across the tetrahedral faces of TTM with no redox changes. Further CuI ions can be added to the [Cu6(MoS4)] moiety to produce cluster ions. This illustrates the ability of the thiometallates to act as building blocks for a very wide range of heterometal complexes ranging from simple linear ions to complex clusters, a prime example of the latter being the FeMo cofactor of the enzyme nitrogenase. TTM was identified sometime ago as the reactive intermediate in the Mo‐induced Cu‐deficiency that afflicts ruminants with serious consequences. Subsequently TTM, as its ammonium salt, has been successfully used in removing the excess Cu and then controlling the Cu levels of patients of Wilson’s disease. It appears to act by blocking the intestinal absorption of Cu and by converting Cu into a metabolically inert form, and in these respects is different to the mode of action of chelating agents which can be used for treating this disease.

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Section: Redox Activitymentioning

confidence: 99%

Thiomolybdates — Simple but Very Versatile Reagents

Laurie

2000

Eur. J. Inorg. Chem.

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“…These compounds are usually obtained by two basic methods: oxidation of µ‐S ligands by strong oxidising agents (e.g., O 2 , H 2 O 2 , NOPF 6 ) or direct inclusion of a SO 2 molecule in the metal cluster . Compounds containing µ‐SO ligands bonded to the transition metal are more exotic because of the instability of the SO moiety and some special conditions (inert atmosphere, low temperatures, etc) should be used to obtain them . In contrast, mixtures M1 and M2 were obtained in air at elevated temperature.…”

Section: Resultsmentioning

confidence: 99%

Reversible Redox Transformations of Bridging Sulfide Ligands within Bioctahedral Rhenium Cluster Anions

et al. 2016

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The present study provides new experimental data on the reactivity of sulfur‐based ligands connected to Re atoms. It was recently discovered that oxidation of µ‐S ligands within the bioctahedral [Re12CS14(µ‐S)3(CN)6]6– cluster anion using H2O2 led to the formation of µ‐SO2 and µ‐SO3 products. This work is focused on the investigation of the opposite process – reduction of the [Re12CS14(µ‐SO2)3(CN)6]6– anion to [Re12CS14(µ‐S)3(CN)6]6– by sulfide ions in an aqueous medium under mild conditions. The reduction results in a slow change of the solution colour, making it possible to investigate in detail the intermediate products. Analysis of the reaction mixture by ESI mass spectrometry revealed that a series of cluster anions [Re12CS17On(CN)6]6– (n = 0–5) was generated during the process. This indicates stepwise chemical reduction of bridging SO2 ligands proceeding through the formation of µ‐SO ligands. In this way, twelve‐nuclear rhenium clusters demonstrate a unique, fully reversible redox cycle of their µ‐bridging ligands, keeping the cluster core unchanged. Two mixed‐ligand cluster anions, [Re12CS14(µ‐SO2)2(µ‐S)(CN)6]6– and [Re12CS14(µ‐SO2)(µ‐S)2(CN)6]6–, were found to be the major reaction intermediates. The former was crystallised with [Cu(NH3)5]2+ and [Cd(NH3)n]2+ ammine cations and investigated by single‐crystal X‐ray diffraction. To understand the electronic structure and charge distribution in [Re12CS17On(CN)6]6– cluster anions, DFT calculations were also carried out.

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“…We have also examined the reactivity of our novel cis-thiohy- , [89] a rare example of a structurally characterized thioperoxide complex. [101][102][103][104] Significantly, addition of excess CO to 47 results in O-atom abstraction and re-formation of the terminal sulfide 32, along with CO 2 . In principle, this series of transformations describes a catalytic cycle for N 2 O reduction (Scheme 12).…”

Section: Group 10mentioning

confidence: 99%

Progress toward the Isolation of Late Metal Terminal Sulfides

Cinco

Hayton

2020

Eur J Inorg Chem

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This Minireview examines the synthesis and characterization of late metal (i.e., groups 8-12) terminal sulfides, along with a discussion of their electronic structures. We discuss both examples where a terminal sulfide was isolated, as well as those examples where a terminal sulfide was invoked as an unobserved intermediate. Additionally, where appropriate, we contextualize our discussion by comparisons to either early [a] M.

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Oxidation at a Dimolybdenum(V) Sulfur Bridge. Formation of SO and SO₂ Bridges. Facile Extrusion of SO from the SO₂ Bridge

Cited by 22 publications

References 68 publications

Thiomolybdates — Simple but Very Versatile Reagents

Thiomolybdates — Simple but Very Versatile Reagents

Reversible Redox Transformations of Bridging Sulfide Ligands within Bioctahedral Rhenium Cluster Anions

Progress toward the Isolation of Late Metal Terminal Sulfides

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Oxidation at a Dimolybdenum(V) Sulfur Bridge. Formation of SO and SO2 Bridges. Facile Extrusion of SO from the SO2 Bridge

Cited by 22 publications

References 68 publications

Thiomolybdates — Simple but Very Versatile Reagents

Thiomolybdates — Simple but Very Versatile Reagents

Reversible Redox Transformations of Bridging Sulfide Ligands within Bioctahedral Rhenium Cluster Anions

Progress toward the Isolation of Late Metal Terminal Sulfides

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Product

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Oxidation at a Dimolybdenum(V) Sulfur Bridge. Formation of SO and SO₂ Bridges. Facile Extrusion of SO from the SO₂ Bridge