Synthesis of polydentate chalcogen-containing ligands using the system hydrazine hydrate–base

Леванова, Е. П.; Vilms, A. I.; Bezborodov, V. A.; Babenko, I. A.; Sosnovskaya, Nina; Istomina, N. V.; Албанов, А. И.; Russavskaya, N. V.; Розенцвейг, И. Б.

doi:10.1134/s1070363217030069

Cited by 11 publications

(9 citation statements)

References 20 publications

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“…In general, chalcogenides have a tendency to form element–element bonds under polymerization or ring-closure reactions, which can be influenced by different parameters such as UV light, pH values, and substituents. − In particular, chalcogenols are prone to form dichalcogenide bonds through oxidation reactions that can be reductively cleaved with a reducing agent such as LiAlH 4 or Zn/NaOH to form reactive chalcogenide species used for the preparation of the corresponding metal chalcogenolates. − Also, zinc treatment under acidic conditions or hydrazine treatment was reported to afford the corresponding chalcogenols. ,, …”

Section: Resultsmentioning

confidence: 99%

Molecular Routes to Two-Dimensional Metal Dichalcogenides MX₂ (M = Mo, W; X = S, Se)

2019

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New synthetic access to two-dimensional transition metal dichalcogenides (TMDCs) is highly desired to exploit their extraordinary semiconducting and optoelectronic properties for practical applications. We introduce here an entirely novel class of molecular precursors, [MIV(XEtN(Me)EtX)2] (MIV = MoIV, WIV, X = S, Se), enabling chemical vapor deposition of TMDC thin films. Molybdenum and tungsten complexes of dianionic tridentate pincer-type ligands (HXEt)2NR (R = methyl, tert-butyl, phenyl) produced air-stable monomeric dichalcogenide complexes, [W(SEtN(Me)EtS)2] and [Mo(SEtN(Me)EtS)2], displaying W and Mo centers in an octahedral environment of 4 S and 2 N donor atoms. Owing to their remarkable volatility and clean thermal decomposition, both Mo and W complexes, when used in the chemical vapor deposition (CVD) process, produced crystalline MoS2 and WS2 thin films. X-ray diffraction analysis and atomic-scale imaging confirmed the phase purity and 2D structural characteristics of MoS2 and WS2 films. The new set of ligands presented in this work open ups convenient access to a scalable and precursor-based synthesis of 2D transition metal dichalcogenides.

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Section: Resultsmentioning

confidence: 99%

Molecular Routes to Two-Dimensional Metal Dichalcogenides MX₂ (M = Mo, W; X = S, Se)

2019

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“…Two well-known methods of synthesis were employed based on bis(2-chloroethyl) ether, thiols, or diorganyldisulfides in the presence of KOH or hydrazine hydrate/base. [60][61][62][63] Methyl-and ethylsubstituted oxadithioethers (L1, L2) were synthesized by the reaction of potassium alkyl sulfides prepared by the reaction of R 2 S 2 (R = Me, Et) and hydrazine hydrate/ KOH with chlorex (Scheme 1). The reaction of bis (2-chloroethyl) ether with RSH/KOH produced other oxadithioethers L3-L8.…”

Section: Synthesis Of Oxadithioether Ligandsmentioning

confidence: 99%

“…The oxadithioethers L3, L4, and L6 are new compounds, whereas L1, L2, L5, L7, and L8 are known. [45,[60][61][62][64][65][66][67][68] The compounds were fully characterized by NMR and Fourier-transform infrared spectroscopy (FTIR). Purity of the obtained ligands was confirmed by GC.…”

Section: Synthesis Of Oxadithioether Ligandsmentioning

confidence: 99%

Synthesis of mononuclear and dinuclear palladium (II) complexes containing oxadithioether ligands and their catalytic activities in norbornene polymerization

Suslov

Abramov

Babenko

et al. 2021

Applied Organom Chemis

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The Pd (II) complexes trans-[PdCl 2 (μ-L)] 2 and [Pd(acac)(L)][BF 4 ] (L = RS (CH 2 ) 2 O(CH 2 ) 2 SR, R = Me, Et, n Pr, i Pr, n Bu, i Bu, n-hexyl, benzyl) were obtained through the reaction of Pd(cod)Cl 2 or [Pd(acac)(MeCN) 2 ][BF 4 ] with one equivalent of oxadithioether (L). The structural features of these complexes were analyzed by nuclear magnetic resonance (NMR) and Fouriertransform infrared spectroscopy (FTIR), as well as electrospray ionisation mass spectrometry and density functional theory calculations. The complexes diμ-(2,10-dimethyl-6-oxa-3,9-dithiaundecane-κ 2 S,S 0 )-bis[trans-dichloropalladium (II)] and (acetylacetonate-κ 2 O,O 0 )(2,10-dimethyl-6-oxa-3,9-dithiaundecane-κ 2 S, S 0 )palladium (II) tetrafluoroborate were characterized by X-ray diffractometry. The X-ray structures of each complex indicate an axial M-O interaction formed by the endodentate conformation of the oxadithioether ligand. Palladium (II) dichloride complexes with oxadithioethers were demonstrated to have a 16-membered dinuclear structure with a trans-configured S 2 PdCl 2 fragment. In the case of cationic palladium acetylacetonate complexes, only mononuclear complexes with a cis configuration of the oxadithioether fragment were observed. Variable temperature 1 H and 13 C NMR studies of the complexes demonstrate dynamic bonding of the oxadithioether ligands consistent with the presence of diastereoisomers that differ in the orientation of the S-R groups along with both endodentate and exodentate bonding modes in solution. FTIR studies of the complexes indicate the presence of isomers in the solid state. The palladium catalyst precursors trans-[PdCl 2 (μ-L)] 2 and [Pd (acac)(L)][BF 4 ] were found to be active in the addition polymerization of norbornene. In the presence of cocatalysts, such as diisobutylaluminum chloride and boron trifluoride etherate, Pd (II) complexes exhibited activities in the range of 10 5 to 10 7 g of polymer (mol of Pd) À1 h À1 . The catalyst systems

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“…Согласно анализу литературных данных, из халькогенидных производных практическое применение пока нашли только органические соединения серы [2,3,5], причем эффективность использования, например, серасодержащих полимерных сорбентов [6] не уступает эффективности широко применяемых ионообменных смол [7], но серасодержащие сорбенты зачастую выгодно отличаются от них по стоимости. Кроме указанных областей использования олигомерные продукты, содержащие халькогены, нашли применение в качестве герметиков (серасодержащие олигомеры) [8], они весьма перспективны для создания парамагнитных материалов (теллурсодержащие олигомеры) [9] и могут применяться в халькогенорганическом синтезе [10][11][12].…”

Section: Introductionunclassified

“…Халькогенорганические олигомеры ранее были получены на основе β,β-дихлордиэтилового эфира (хлорекса) 1 с использованием систем гидразингидрат-основание и элементных халькогенов. Для получения сера-и селенсодержащих олигомеров были использованы три основно-восстановительные системы: гидразингидрат-моноэтаноламин (МЭА), (получены олигомеры 2а и 3а) [12,13], гидразингидрат-вода-КОН (получены олигомеры 2б и 3б) [13], гидразингидрат-КОН, без добавления воды (олигомер 4) [14]. Было также обнаружено, что сера-и селенсодержащие олигомеры 2а и 3а хорошо растворяются в таких органических растворителях, как хлороформ, ацетон, диоксан и др.…”

Section: Introductionunclassified

The effect of the nature of the сhalcogen atom on the extraction and adsorption characteristics of chalcogen-containing oligomers based on chlorex

Алтынникова

Grabel’nykh

Руссавская

et al. 2021

Izvestiâ vuzov. Prikladnaâ himiâ i biotehnologiâ

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The extraction and adsorption characteristics of chalcogen-containing oligomers derived from chlorex and elemental chalcogens in the hydrazine hydrate–base systems were studied. Sulphur- and selenium-containing oligomers synthesised in hydrazine hydrate–monoethanolamine systems are soluble in organic solvents. The as-obtained solutions are capable of extracting the following ions from water solutions: Hg2+, Cd2+, Zn2+, Pb2+, Cu2+ and Ni2+. Oligomers synthesised in the hydrazine hydrate–water–KOH system (sulphur- and selenium-containing oligomers) and a tellurium-containing oligomer obtained in the hydrazine hydrate–KOH system were used as adsorbents. It was assumed that the extraction and adsorption of metal ions by chalcogen-containing oligomers is carried out through the formation of complexes in which the chalcogen atoms act as ligands. The effect of the nature of chalcogen atoms on the possibility of forming complexes, i.e. on the extraction and adsorption properties of the oligomers used, was considered using the theory of hard and soft acids and bases (HSAB). According to this theory, the cations Hg2+ and Cd2+ belong to soft acids, while the cations Zn2+, Pb2+, Cu2+ and Ni2+ belong to acids of intermediate hardness. Chalcogen atoms are classified as soft bases. The conducted experiment showed that Hg2+ and Cd2+ ions are easily extracted and adsorbed by all the oligomers used, while the intermediate-hardness cations most easily interact with the sulphur-containing oligomers. The formation of oligomer–metal complexes was confirmed by analysing IR and 77Se NMR spectra recorded for sulphur- and selenium-containing oligomers before and after the extraction. The recorded IR spectra contained obvious changes in the nature of the absorption bands due to the stretching vibrations of the C–S and C–Se bonds. An additional signal of de-screened selenium nuclei was observed in the 77Se NMR spectrum. An insignificant change in the nature of the IR spectra in the region of stretching C–O vibrations indicated a weak participation of oxygen in the formation of complexes. It can be assumed that the role of oxygen in maintaining the high rates of extraction and adsorption is associated with an increase in the flexibility of macromolecules, which ensures a more favourable geometry for complex formation.

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Synthesis of polydentate chalcogen-containing ligands using the system hydrazine hydrate–base

Cited by 11 publications

References 20 publications

Molecular Routes to Two-Dimensional Metal Dichalcogenides MX₂ (M = Mo, W; X = S, Se)

Molecular Routes to Two-Dimensional Metal Dichalcogenides MX₂ (M = Mo, W; X = S, Se)

Synthesis of mononuclear and dinuclear palladium (II) complexes containing oxadithioether ligands and their catalytic activities in norbornene polymerization

The effect of the nature of the сhalcogen atom on the extraction and adsorption characteristics of chalcogen-containing oligomers based on chlorex

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Synthesis of polydentate chalcogen-containing ligands using the system hydrazine hydrate–base

Cited by 11 publications

References 20 publications

Molecular Routes to Two-Dimensional Metal Dichalcogenides MX2 (M = Mo, W; X = S, Se)

Molecular Routes to Two-Dimensional Metal Dichalcogenides MX2 (M = Mo, W; X = S, Se)

Synthesis of mononuclear and dinuclear palladium (II) complexes containing oxadithioether ligands and their catalytic activities in norbornene polymerization

The effect of the nature of the сhalcogen atom on the extraction and adsorption characteristics of chalcogen-containing oligomers based on chlorex

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Molecular Routes to Two-Dimensional Metal Dichalcogenides MX₂ (M = Mo, W; X = S, Se)

Molecular Routes to Two-Dimensional Metal Dichalcogenides MX₂ (M = Mo, W; X = S, Se)