Tetraethylammonium Hydrogen Sulfide: A Convenient Reagent for Thiolation of 1,1-Dichloroalkenes

Schaumann, Ernst; Wriede, Ulrich; Ehlers, J.

doi:10.1055/s-1980-29265

Cited by 24 publications

(9 citation statements)

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“…Our first indication of the existence of Fe–NR–S cubanes came from investigation of the synthesis of dinuclear 2 , where the use of other sulfide sources (Na 2 S, NaSH, (Et 4 N)SH) in place of (Me 3 Si) 2 S gave product mixtures from which imide–sulfide cubanes were identified. Further study and optimization led to reaction of 1 with 0.5 equiv of (Et 4 N)SH, which directly forms the triimide monosulfide cubane 8 . In our preliminary report, twice the amount of (Et 4 N)SH (1 equiv) was employed, but we found inconsistent product selectivity at this stoichiometry.…”

Section: Resultsmentioning

confidence: 99%

Iron–Amide–Sulfide and Iron–Imide–Sulfide Clusters: Heteroligated Core Environments Relevant to the Nitrogenase FeMo Cofactor

et al. 2012

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Heteroligated cluster cores consisting of weak-field iron, strongly basic nitrogen anions, and sulfide are of interest with respect to observed and conjectured environments in the FeMo cofactor of nitrogenase. Selective syntheses have been developed to achieve such environments with tert-butyl-substituted amide and imide core ligands. A number of different routes were employed, including nominal ligand substitution and oxidative addition reactions, as well as novel transformations involving the combination of different cluster precursors. New cluster products include precursor Fe(2)(μ-NH(t)Bu)(2)[N(SiMe(3))(2)](2) (6), Fe(2)(μ-NH(t)Bu)(2)(μ-S)[N(SiMe(3))(2)](2) (7), which has a rare confacial bitetrahedral geometry previously unknown in iron chemistry, [Fe(2)(μ-N(t)Bu)(μ-S)Cl(4)](2-) (2), and cuboidal [Fe(4)(μ(3)-N(t)Bu)(3)(μ(3)-S)Cl(4)](-) (8), [Fe(4)(μ(3)-N(t)Bu)(2)(μ(3)-S)(2)Cl(4)](2-) (9), and [Fe(4)(μ(3)-N(t)Bu)(μ(3)-S)(3)Cl(4)](2-) (10), as well as selenide-substituted derivatives Fe(2)(μ-NH(t)Bu)(2)(μ-Se)[N(SiMe(3))(2)](2) (7-Se) and [Fe(4)(μ(3)-N(t)Bu)(μ(3)-Se)(3)Cl(4)](2-) (10-Se). The imide-sulfide clusters complete the compositional sets [Fe(2)(μ-N(t)Bu)(n)(μ-S)(2-n)Cl(4)](2-) (n = 0-2) and [Fe(4)(μ(3)-N(t)Bu)(n)(μ(3)-S)(4-n)Cl(4)](z) (n = 0-4), represented previously only by the all-imide and all-sulfide core congeners, and they share chemical and physical properties with the parent homoleptic core species. All imide-sulfide cores are compositionally stable and show no evidence of core ligand exchange over days in solution. Beyond structural differences, the impact of mixed core ligation is most evident in redox potentials, which show progressive decreases of -435 (for z = 1-/2-) or -385 mV (for z = 2-/3-) for each replacement of sulfide by the more potent imide donor, and a corresponding effect may be expected for the interstitial heteroligand in the FeMo cofactor. Cluster 10 presents an [Fe(4)NS(3)] core framework virtually isometric with the isostructural [Fe(4)S(3)X] subunit of the FeMo cofactor, thus providing a synthetic structural representation for this portion of the cofactor core.

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Section: Resultsmentioning

confidence: 99%

Iron–Amide–Sulfide and Iron–Imide–Sulfide Clusters: Heteroligated Core Environments Relevant to the Nitrogenase FeMo Cofactor

et al. 2012

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“…An exception to this are the tetraalkylammonium hydrosulfides (especially alkyl=methyl, ethyl, butyl), which have been known since the 1960s, but were never characterized in detail . They are primarily employed as reagents in the synthesis of transition‐metal complexes and clusters, the application in organic thiolation reactions was described several decades ago …”

Section: Introductionmentioning

confidence: 99%

Halide‐Free Synthesis of Hydrochalcogenide Ionic Liquids of the Type [Cation][HE] (E=S, Se, Te)

Finger

2016

Chemistry A European J

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We present the synthesis and thorough characterization of ionic liquids and organic salts based on hydrochalcogenide HE(-) (E=S, Se, Te) anions. Our approach is based on halide-, metal-, and water-free decarboxylation of methylcarbonate precursors under acidic conditions, resulting from the easily dissociating reagents H2 E. The compounds were characterized by elemental analysis, multinuclear NMR spectroscopy, thermal and single-crystal XRD analyses. The hydrosulfide salts were investigated with respect to their ability to dissolve elemental sulfur in varying stoichiometry. Thus-prepared polysulfide ILs were also analyzed by UV/Vis spectroscopy and cyclic voltammetry.

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“…Use of tetraalkylammonium cations to enhance the solubility of HS − in organic solution has been cited since the 1960s, however most reported syntheses rely on in situ salt generation or reaction of H 2 S gas with tetralkylammonium hydroxides. 18 Such preparative methods introduce complications involving removal of the water by-product in the case of hydroxide precursors, 19 and limit the reaction scale in cases where H 2 S gas is employed. 20 Additionally, compounds prepared in this fashion suffer from limited product characterization, and previouslyavailable commercial sources of NBu 4 SH were not of analytical purity.…”

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confidence: 99%

NBu₄SH provides a convenient source of HS⁻ soluble in organic solution for H₂S and anion-binding research

et al. 2015

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Hydrogen sulfide (H2S) has gained significant interest within the scientific community due to its expanding roles in different (patho)physiological processes. Despite this importance, the chemical mechanisms by which H2S exerts its action remain under-scrutinized. Biomimetic investigations in organic solution offer the potential to clarify these mechanisms and to delineate the differential reactivity between H2S and HS(-). However, such studies are hampered by the lack of readily-available sources of HS(-) that are soluble in organic solution. Here we present a simple method for preparing analytically pure tetrabutylammonium hydrosulfide (NBu4SH), which we anticipate will be of significant utility to researchers in the H2S and anion-binding communities.

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Tetraethylammonium Hydrogen Sulfide: A Convenient Reagent for Thiolation of 1,1-Dichloroalkenes

Cited by 24 publications

References 0 publications

Iron–Amide–Sulfide and Iron–Imide–Sulfide Clusters: Heteroligated Core Environments Relevant to the Nitrogenase FeMo Cofactor

Iron–Amide–Sulfide and Iron–Imide–Sulfide Clusters: Heteroligated Core Environments Relevant to the Nitrogenase FeMo Cofactor

Halide‐Free Synthesis of Hydrochalcogenide Ionic Liquids of the Type [Cation][HE] (E=S, Se, Te)

NBu₄SH provides a convenient source of HS⁻ soluble in organic solution for H₂S and anion-binding research

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Tetraethylammonium Hydrogen Sulfide: A Convenient Reagent for Thiolation of 1,1-Dichloroalkenes

Cited by 24 publications

References 0 publications

Iron–Amide–Sulfide and Iron–Imide–Sulfide Clusters: Heteroligated Core Environments Relevant to the Nitrogenase FeMo Cofactor

Iron–Amide–Sulfide and Iron–Imide–Sulfide Clusters: Heteroligated Core Environments Relevant to the Nitrogenase FeMo Cofactor

Halide‐Free Synthesis of Hydrochalcogenide Ionic Liquids of the Type [Cation][HE] (E=S, Se, Te)

NBu4SH provides a convenient source of HS− soluble in organic solution for H2S and anion-binding research

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Product

Resources

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NBu₄SH provides a convenient source of HS⁻ soluble in organic solution for H₂S and anion-binding research