Selenium chloride and bromide equilibria in aprotic solvents; a 77Se NMR study

Lamoureux, Marc; Milne, J. B.

doi:10.1016/s0277-5387(00)86238-5

Cited by 62 publications

(40 citation statements)

References 13 publications

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“…The other strong signals neighbouring these ClSeSeBr peaks are due to the parent dichloride (1 285.6 ppm) and dibromide (1 186.9 ppm), which lie slightly more shielded than in the pure liquids. The assignment of these four diselenium dihalide signals parallels that observed for mixtures of Se2Cl2/Se,Br2 in CH2C1, (6) and suggests that the assignment of the signals for Se attached to C1 for ClSeSeCl and ClSeSeBr in the Se2C1,/SezBr2 mixture (2) may be reversed. From the relative chemical shifts of Se2C1, and SeSC1, in the Se2C12/S2C12 mixture, the signal at 1298.3 ppm is assigned to SeSCl, and the remaining peak in the Se bound to C1 part of the spectrum (1313.0 ppm) Can From a comparison of the relative intensities of the signal of Se attached to Br to those of the Se attached to C1, it is apparent that most of the Se is bound to Br and the S to C1.…”

Section: Selenium-77 Nmr Spectroscopysupporting

confidence: 68%

“…Early dipole moment studies of benzene solutions suggested that Se,Cl, may also have a pyramidal form (17) but these observations are probably accounted for by the presence of equilibrium amounts of SeCl,, Se3Cl,, and Se,Cl, in these solutions (6) and all the evidence supports a chain structure for this molecule (8,18). Seleninyl chloride, SeOCl,, has a pyramidal form (19) but this work has shown that SeSCl,, prepared by equilibration of SzClz and Se,Cl, mixtures, has a chain structure.…”

Section: Resultsmentioning

confidence: 99%

“…The decreased shielding resulting from decreased electron density at the Se nucleus is usually assumed to be dominated by the paramagnetic contribution (14). The chemical shifts of the Se,X, and Sex, (X = Br, C1) follow this rule in general (2,6). For the same halogens, the signal of the Se(I1) species is several hundred ppm deshielded compared to the Se(1) species (SeCl,: 1730.7 ppm; Se,Cl,: 1291.3 ppm; SeBr,: 1467.7 ppm; Se,Br,: 1192.7 ppm; SeBrC1: 1600.7 ppm; mean of Se,BrCl: 1248.7 ppm).…”

Section: Selenium-77 Nmr Spectroscopymentioning

confidence: 99%

“…and Se,CI, with S was undertaken as part of an ongoing study of low-valent Se halide chemistry (2,6).…”

Section: Introductionmentioning

confidence: 99%

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Selenium sulfur dihalides, Ch_nX₂ (n = 1, 2, 3; Ch = Se, S; X = Br, Cl). Raman and ⁷⁷Se NMR spectroscopic characterization

Milne¹

1992

Can. J. Chem.

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in SezClz have been studied by Raman and 17se NMR spectroscopy. Selenium sulfur dihalides, SeSCl,, SeSBr,, and SeSBrC1, formed in these solutions, have been shown by Raman and 17se NMR spectroscopy to have chain structures. Solutions of Se,C12 in S2C12, S in Se,CI,, and Se in S2CI2 have been shown to contain, in addition to Se,Cl,, S2C12, SeSCI,, Se3C1,, and S8, trichalcogen dichlorides Se2SCI2 and SeS2C1,. Selenium-77 signals corresponding to all seven chain isomers of the expected Se-containing dichalcogen dihalides, SezBr2, SeZC1,, Se,BrCI, SeSC12, SeSBr,, BrSeSCl, and CISeSBr, have been observed in the spectrum of a 1 : 1 molar mixture of S2C1, and Se,Br,. The disulfur dichloride and dibromide, as well as the bromide chloride, are also present. Selenium-bromine and sulfur-chlorine linkages are observed to be preferred over selenium-chlorine and sulfur-bromine bonding in these mixtures. The 17se chemical shifts correlate well with the electronegativity of the directly bonded neighbour but inversely with that of the next-nearest neighbour.Key words: selenium halides, sulfur halides, low valent chalcogen halides, 17se NMR, Raman spectroscopy.

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Section: Selenium-77 Nmr Spectroscopysupporting

confidence: 68%

Section: Resultsmentioning

confidence: 99%

Section: Selenium-77 Nmr Spectroscopymentioning

confidence: 99%

“…and Se,CI, with S was undertaken as part of an ongoing study of low-valent Se halide chemistry (2,6).…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Selenium sulfur dihalides, Ch_nX₂ (n = 1, 2, 3; Ch = Se, S; X = Br, Cl). Raman and ⁷⁷Se NMR spectroscopic characterization

Milne¹

1992

Can. J. Chem.

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“…The proton NMR spectrum of solutions of 2-mercaptoethanol oxidized with Se02 (weakly basic conditions), 13-and H202 with oxidant/HOC2H4SH stoichiometries of 1:4, 1:2, and 1:2 respectively, do not show a signal, corresponding to hydrogen bound to sulfur and oxida-. -tion to the disilfide complete via reactions [3], [5], and [6].…”

Section: Nmr Spectroscopymentioning

confidence: 99%

Studies on the interaction of selenite and selenium with sulphur donors. Part 1. 2-Mercaptoethanol

Amaratunga¹,

Chaudry²,

Milne³

1994

Can. J. Chem.

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Raman spectroscopy and proton and 77Se NMR have been used to show that selenous acid reacts with 2-mercaptoethanol (HOC2H4SH), according to Ganther's reaction (H.E. Ganther, Biochemistry, 7, 2898 (1968)).[Formula: see text]The bis(hydroxyethylthio)selenide decomposes readily in strongly acidic and moderately basic solution to selenium and disulfide,[Formula: see text]Selenium dissolves in excess hydroxyethylmercaptide to give the catenated anion, HOC2H4SSe−[Formula: see text]Air oxidation of this equilibrium mixture yields disulfide and selenium. Formation of the hydroxyethylthioselenide is endothermic (ΔH = 0.66 ± 0.02 kJ mol−1).

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Selenium‐NMR Spectroscopy in Organic Synthesis: From Structural Characterization Toward New Investigations

et al. 2020

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This review article deals with organic synthesis from the perspective of selenium-77 nuclear magnetic resonance (NMR) spectroscopy. Different types of organic reactions are briefly discussed, incorporating mechanism aspects through 77 Se NMR observable intermediates and byproducts. The 77 Se NMR experiments are demonstrated in terms of structural characterization and new insights for organic reactions. The ability to visualize different molecules in a reaction mixture provides a facile and versatile route for the development of synthetic organoselenium compounds. Thus, the review describes the strategies accomplished mainly in the past five years in the syntheses and applications of the organoselenium compounds, focusing on 77 Se NMR spectroscopy.

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Selenium chloride and bromide equilibria in aprotic solvents; a 77Se NMR study

Cited by 62 publications

References 13 publications

Selenium sulfur dihalides, Ch_nX₂ (n = 1, 2, 3; Ch = Se, S; X = Br, Cl). Raman and ⁷⁷Se NMR spectroscopic characterization

Selenium sulfur dihalides, Ch_nX₂ (n = 1, 2, 3; Ch = Se, S; X = Br, Cl). Raman and ⁷⁷Se NMR spectroscopic characterization

Studies on the interaction of selenite and selenium with sulphur donors. Part 1. 2-Mercaptoethanol

Selenium‐NMR Spectroscopy in Organic Synthesis: From Structural Characterization Toward New Investigations

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Selenium chloride and bromide equilibria in aprotic solvents; a 77Se NMR study

Cited by 62 publications

References 13 publications

Selenium sulfur dihalides, ChnX2 (n = 1, 2, 3; Ch = Se, S; X = Br, Cl). Raman and 77Se NMR spectroscopic characterization

Selenium sulfur dihalides, ChnX2 (n = 1, 2, 3; Ch = Se, S; X = Br, Cl). Raman and 77Se NMR spectroscopic characterization

Studies on the interaction of selenite and selenium with sulphur donors. Part 1. 2-Mercaptoethanol

Selenium‐NMR Spectroscopy in Organic Synthesis: From Structural Characterization Toward New Investigations

Contact Info

Product

Resources

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Selenium sulfur dihalides, Ch_nX₂ (n = 1, 2, 3; Ch = Se, S; X = Br, Cl). Raman and ⁷⁷Se NMR spectroscopic characterization

Selenium sulfur dihalides, Ch_nX₂ (n = 1, 2, 3; Ch = Se, S; X = Br, Cl). Raman and ⁷⁷Se NMR spectroscopic characterization