Generation and Spectroscopic Identification of the Thiuram Radical (CH3)2NCS2

Mardyukov, Artur; Keul, Felix; Schreiner, Peter R.

doi:10.1021/acs.jpca.9b03307

Cited by 3 publications

(3 citation statements)

References 38 publications

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“…It is not easy to distinguish these events, but given that zinc has no redox 378 which would be formed via route (ii) upon addition of the alkyl radical to a thiuram radical. Interestingly, the thiuram radical, S 2 CNMe 2 , has recently been isolated and spectroscopically characterized by Mardyukov and co-workers being formed upon flash vacuum pyrolysis of Me 4 -TDS at 600 °C, followed by irradiation at λ = 623 nm in an argon matrix at 10 K. 62 The S−S bond dissociation enthalpy of Me 4 -TDS is ca. 146 kJ mol −1 , and hence formation of TDS from the DTC radicals would not be expected at high temperatures.…”

Section: Groupmentioning

confidence: 99%

“…Interestingly, the thiuram radical, S 2 CNMe 2 , has recently been isolated and spectroscopically characterized by Mardyukov and co-workers being formed upon flash vacuum pyrolysis of Me 4 -TDS at 600 °C, followed by irradiation at λ = 623 nm in an argon matrix at 10 K . The S–S bond dissociation enthalpy of Me 4 -TDS is ca.…”

Section: Binary Sulfidesmentioning

confidence: 99%

“…Some standard molar enthalpies of formation and sublimation have been determined, allowing mean molar bond dissociation energies to be derived or estimated . In the gas phase, homolytic metal–sulfur bond scission, to generate an S 2 CNR 2 radical, is significantly more favorable than heterolytic cleavage, being estimated at 143 and 678 kJ mol –1 , respectively, for [Cu(S 2 CNEt 2 ) 2 ] . For diethyl–DTC complexes, the following trends have been established for the homolytic cleavage of metal–sulfur bonds: M(III), Cr > Co > Mn ≅ Fe; M(II), Ni > Cu > Zn > Pd > Cd, although it is worth emphasizing that the range is relatively small .…”

Section: Introductionmentioning

confidence: 99%

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Dithiocarbamate Complexes as Single Source Precursors to Nanoscale Binary, Ternary and Quaternary Metal Sulfides

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Nanodimensional metal sulfides are a developing class of low-cost materials with potential applications in areas as wide-ranging as energy storage, electrocatalysis, and imaging. An attractive synthetic strategy, which allows careful control over stoichiometry, is the single source precursor (SSP) approach in which well-defined molecular species containing preformed metal–sulfur bonds are heated to decomposition, either in the vapor or solution phase, resulting in facile loss of organics and formation of nanodimensional metal sulfides. By careful control of the precursor, the decomposition environment and addition of surfactants, this approach affords a range of nanocrystalline materials from a library of precursors. Dithiocarbamates (DTCs) are monoanionic chelating ligands that have been known for over a century and find applications in agriculture, medicine, and materials science. They are easily prepared from nontoxic secondary and primary amines and form stable complexes with all elements. Since pioneering work in the late 1980s, the use of DTC complexes as SSPs to a wide range of binary, ternary, and multinary sulfides has been extensively documented. This review maps these developments, from the formation of thin films, often comprised of embedded nanocrystals, to quantum dots coated with organic ligands or shelled by other metal sulfides that show high photoluminescence quantum yields, and a range of other nanomaterials in which both the phase and morphology of the nanocrystals can be engineered, allowing fine-tuning of technologically important physical properties, thus opening up a myriad of potential applications.

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Section: Groupmentioning

confidence: 99%

Section: Binary Sulfidesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Dithiocarbamate Complexes as Single Source Precursors to Nanoscale Binary, Ternary and Quaternary Metal Sulfides

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Synthesis of 2‐Aryl‐2‐hydroxyethyl Dithiocarbamates via Regioselective Addition of Tetraalkylthiuram Disulfides to Styrenes under Transition‐Metal‐Free Conditions

et al. 2020

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This paper describes a method for the synthesis of 2-aryl-2-hydroxyethyl dithiocarbamates via difunctionalization of alkenes involving CÀ S and CÀ O bonds formation with tetraalkylthiuram disulfides as the functional reagents. The reaction proceeded well under transition-metal-free conditions and afforded up to 88% yield of the desired products. Numerous useful functional groups were tolerated under the reaction conditions. This methodology provides a direct approach to β-hydroxy dithiocarbamates, featuring readily available starting materials and broad substrate scope, which shows its practical synthetic value in organic synthesis.

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Spectroscopic identification of the phenyltelluryl radical and its reactivity toward molecular oxygen

Keul

Mardyukov

Schreiner

2019

Phys. Chem. Chem. Phys.

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Generation and Spectroscopic Identification of the Thiuram Radical (CH₃)₂NCS₂

Cited by 3 publications

References 38 publications

Dithiocarbamate Complexes as Single Source Precursors to Nanoscale Binary, Ternary and Quaternary Metal Sulfides

Dithiocarbamate Complexes as Single Source Precursors to Nanoscale Binary, Ternary and Quaternary Metal Sulfides

Synthesis of 2‐Aryl‐2‐hydroxyethyl Dithiocarbamates via Regioselective Addition of Tetraalkylthiuram Disulfides to Styrenes under Transition‐Metal‐Free Conditions

Spectroscopic identification of the phenyltelluryl radical and its reactivity toward molecular oxygen

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