Communications- Organic Disulfides and Related Substances. V. The Eight-Membered Ring System Bis(o-phenylene) Tetrasulfide.

Field, Lamar; Stephens, William D.; Lippert, Ernest L.

doi:10.1021/jo01069a610

Cited by 24 publications

(8 citation statements)

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“…Compound 6 is a coproduct that was obtained with 4 and 5 due to the presence of the free ligand that was generated by the formation of cluster 5 . In fact, the formation of the eight‐membered bis(disulfide) rings from the reaction of the ortho ‐dithiolates is not unprecedented 14. The crystal structure of 6 revealed a 50 % cis ‐ trans disorder of the thiophene rings in a chair‐type conformation, as was previously observed for bis( o ‐phenylene) bis(sulfide) (see Supporting Information, Figure S10) 15.…”

Section: Resultssupporting

confidence: 55%

Ni‐2,3‐thiophenedithiolate Anions in New Architectures: An In‐Line Mixed‐Valence Ni Dithiolene (Ni₄–S₁₂) Cluster

Neves¹,

Santos²,

Pereira³

et al. 2011

Eur J Inorg Chem

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A family of salts that was based on the [Ni(α-tpdt) n-anions (α-tpdt = 2,3-thiophenedithiolate) and the K + crown-ether cations were prepared and were then structurally and magnetically characterised. In [K(18-crown-6)][Ni(α-tpdt) 2 ], the anion has a square planar coordination geometry with ligand disorder and the cations and anions are segregated in alternating layers in the crystal structure, as was found in the previous [Ni(α-tpdt) 2 ] -salts. Two salts were obtained with the [K(15-crown-5) 2 ] + cation. The expected 1:1 salt was obtained, which had the usual anion square planar coordination geometry for [Ni(α-tpdt) 2 ] -but that had a new molecular arrangement based on an anion double chain. In addition, a 2:1 salt

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Section: Resultssupporting

confidence: 55%

Ni‐2,3‐thiophenedithiolate Anions in New Architectures: An In‐Line Mixed‐Valence Ni Dithiolene (Ni₄–S₁₂) Cluster

Neves¹,

Santos²,

Pereira³

et al. 2011

Eur J Inorg Chem

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“…Last, the utility of 1,2-C 6 H 4 (SSiMe 3 ) 2 as a dithiolene chelate ring precursor is further emphasized by formation of bis-complex 11 (80%) in a procedure more convenient than the published methods. , The reaction, performed with a 3:1 mol ratio of reactants, probably proceeds by the stoichiometry of reaction 7, in which the reductant of Re VII is presumably (di)thiolate generated by Si−S bond cleavage. The sulfur-containing product would then be bis( o -phenylene)tetrasulfide or a disulfide polymer …”

Section: Resultsmentioning

confidence: 99%

“…15,16 The reaction, performed with a 3:1 mol ratio of reactants, probably proceeds by the stoichiometry of reaction 7, in which the reductant of Re VII is presumably (di)thiolate generated by Si-S bond cleavage. The sulfur-containing product would then be bis(o-phenylene)tetrasulfide 48 tungsten, and rhenium by reactions with carbon and silicon electrophiles. These include a monosilylated species (1), monosulfido anions (2, 3, 6, 10), monodithiolene trioxo (4, 7) and dioxo (8) complexes, and bis(dithiolene) dioxo (9) and monooxo (11)…”

Section: Resultsmentioning

confidence: 99%

Oxygen/Sulfur Substitution Reactions of Tetraoxometalates Effected by Electrophilic Carbon and Silicon Reagents

Partyka

Holm

2004

Inorg. Chem.

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Reactions of [MO(4)](2)(-) (M = Mo, W) with certain carbon and silicon electrophiles were investigated in acetonitrile in order to produce species of potential utility in the synthesis of analogues of the sites in the xanthine oxidoreductase enzyme family. Silylation of [MoO(4)](2)(-) affords [MoO(3)(OSiPh(3))](1)(-), which with Ph(3)SiSH is converted to [MoO(2)S(OSiPh(3))](1)(-). Reaction with (Ph(3)C)(PF(6))/HS(-) yields the tetrahedral monosulfido species [MO(3)S](2)(-), previously obtained only from the aqueous system [MO(4)](2)(-)/H(2)S. Dithiolene chelate rings are readily introduced upon reaction with 1,2-C(6)H(4)(SSiMe(3))(2), leading to the square pyramidal trioxo complexes [MO(3)(bdt)](2)(-), a previously unknown dithiolene molecular type. Further ring insertion occurs upon reaction of [WO(3)(bdt)](2)(-) with 1,2-C(6)H(4)(SSiMe(3))(2), giving [WO(2)(bdt)(2)](2)(-). Related reactions occur with [ReO(4)](1)(-). Treatment with 1 equiv of (Me(3)Si)(2)S produces [ReO(3)S](1)(-); with 3 equiv of 1,2-C(6)H(4)(SSiMe(3))(2), [ReO(bdt)(2)](1)(-) is obtained with concomitant Re(VII) --> Re(V) reduction. X-ray structures are reported for [MO(3)S](z)(-) (M = Mo, W, z = 2; M = Re, z = 1), [MO(3)(bdt)](2)(-), and [WO(2)(OSiPh(3))(bdt)](1)(-), a silylation product of [WO(3)(bdt)](2)(-). [MoO(3)(bdt)](2)(-) is related to the site of inactive sulfite oxidase, and [WO(2)(OSiPh(3))(bdt)](1)(-) should closely approximate the metric features of the [(dithiolene)MoO(2)(OH)] site in inactive aldehyde/xanthine oxidoreductase. This work provides convenient syntheses of known and new derivatives of tetraoxometalates, among which is entry to a unique class of oxo-monodithiolene complexes.

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“…Die beiden Molekül-hälften können nämlich gemäß 1 a bzw. 1 b eis-oder trans-artig verknüpft sein, wobei jeweils noch zwei Formen, die starre anti-Form I und die bewegliche syn-Form mit den Grenzkonformationen II a-c [2], diskutiert werden müssen. Um eine eindeutige Strukturzuordnung, die auf anderem Wege nur schwer zu erhalten gewesen wäre, treffen zu können, wurde eine Röntgenstrukturanalyse der Verbindung angefertigt.…”

Section: Introductionunclassified

Chalkogenolat-Ionen und ihre Derivate, V Kristall- und Molekülstruktur von 2.8-Dimethyldibenzo [c.g] [1.2.5.6] tetrathiacyclooktadien, einem Oxidationsprodukt von 4-Methylbenzol-1.2-dithiol/Chalcogenolates and their Derivatives, V Crystal and Molecular Structure of 2.8-Dimethyldibenzo[c,g][1,2,5,6]tetrathiaocin, an Oxidation Product of 4-Methylbenzene-1,2-dithiol

Kopf

Deuten

Nakhdjavan

et al. 1979

Zeitschrift Für Naturforschung B

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Communications- Organic Disulfides and Related Substances. V. The Eight-Membered Ring System Bis(o-phenylene) Tetrasulfide.

Cited by 24 publications

References 0 publications

Ni‐2,3‐thiophenedithiolate Anions in New Architectures: An In‐Line Mixed‐Valence Ni Dithiolene (Ni₄–S₁₂) Cluster

Ni‐2,3‐thiophenedithiolate Anions in New Architectures: An In‐Line Mixed‐Valence Ni Dithiolene (Ni₄–S₁₂) Cluster

Oxygen/Sulfur Substitution Reactions of Tetraoxometalates Effected by Electrophilic Carbon and Silicon Reagents

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Communications- Organic Disulfides and Related Substances. V. The Eight-Membered Ring System Bis(o-phenylene) Tetrasulfide.

Cited by 24 publications

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Ni‐2,3‐thiophenedithiolate Anions in New Architectures: An In‐Line Mixed‐Valence Ni Dithiolene (Ni4–S12) Cluster

Ni‐2,3‐thiophenedithiolate Anions in New Architectures: An In‐Line Mixed‐Valence Ni Dithiolene (Ni4–S12) Cluster

Oxygen/Sulfur Substitution Reactions of Tetraoxometalates Effected by Electrophilic Carbon and Silicon Reagents

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Ni‐2,3‐thiophenedithiolate Anions in New Architectures: An In‐Line Mixed‐Valence Ni Dithiolene (Ni₄–S₁₂) Cluster

Ni‐2,3‐thiophenedithiolate Anions in New Architectures: An In‐Line Mixed‐Valence Ni Dithiolene (Ni₄–S₁₂) Cluster