Synthesis, properties, oxidation, and electrochemistry of 1,2- dichalcogenins

Eric Block, Marc Birringer, Russell Deorazio, Jürgen Fabian, Richard S Glass, Chuangxing Guo, Chunhong He, Edward Lorance, Quangsheng Qian, T. Benjamin Schroeder, Zhixing Shan, Mohan Thiruvazhi, George S. Wilson, Xing Zhang

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Abstract

Syntheses are presented of the 1,2-dichalcogenins: 1,2-dithiin, 1,2- diselenin, and 2-selenathiin, both substituted and unsubstituted. 1,2-Dithiin and 1,2-diselenin are prepared by reaction of PhCH2XNa (X = S or Se) with 1,4-bis(trimethylsilyl)-1,3-butadiyne followed by reductive cleavage and oxidation. 2-Selenathiin is similarly prepared using a mixture of PhCH2SeNa and PhCH2SNa. Reaction of titanacyclopentadienes with (SCN)2 or (SeCN)2 followed by bis(thiocyanate) or bis(selenocyanate) cyclization affords substituted 1,2-dithiins or 1,2-diselenins, respectively. With S2Cl2, 1,2- dithiins are directly formed from titanacyclopentadienes. Oxidation of 1,2- dithiins and 1,2-diselenins gives the corresponding 1-oxide and, with 1,2- dithiins and excess oxidant, 1,1-dioxides; oxidation of 2-selenathiin gives the 2-oxide. Electrochemical oxidation of 1,2-dichalcogenins, which have a twisted geometry, affords planar radical cations by an EC mechanism. One- electron AlCl3 oxidation of 3,6-diphenyl-1,2-dithiin gives the corresponding radical cation, characterized by EPR spectroscopy. Theoretical calculations result in a flattened structure for the 1,2-dithiin radical cation and a fully planar structure for the 1,2-diselenin radical cation. The 77Se NMR chemical shifts of 1,2-diselenin are characteristically high-field-shifted with respect to open chain diselenides in good agreement with results of GIAO-DFT calculations based on MP2 and DFT optimum geometries.

Original languageEnglish (US)
Pages (from-to)5052-5064
Number of pages13
JournalJournal of the American Chemical Society
Volume122
Issue number21
DOIs
StatePublished - May 31 2000

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Electrochemistry
Cations
Positive ions
Oxidation
Discrete Fourier transforms
Oxides
Geometry
Electrochemical oxidation
Cyclization
Chemical shift
Oxidants
Paramagnetic resonance
Spectrum Analysis
Nuclear magnetic resonance
Spectroscopy
Electrons

ASJC Scopus subject areas

  • Chemistry(all)

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Synthesis, properties, oxidation, and electrochemistry of 1,2- dichalcogenins. / Block, Eric; Birringer, Marc; Deorazio, Russell; Fabian, Jürgen; Glass, Richard S; Guo, Chuangxing; He, Chunhong; Lorance, Edward; Qian, Quangsheng; Schroeder, T. Benjamin; Shan, Zhixing; Thiruvazhi, Mohan; Wilson, George S.; Zhang, Xing.

In: Journal of the American Chemical Society, Vol. 122, No. 21, 31.05.2000, p. 5052-5064.

Research output: Contribution to journalArticle

Block, E, Birringer, M, Deorazio, R, Fabian, J, Glass, RS, Guo, C, He, C, Lorance, E, Qian, Q, Schroeder, TB, Shan, Z, Thiruvazhi, M, Wilson, GS & Zhang, X 2000, 'Synthesis, properties, oxidation, and electrochemistry of 1,2- dichalcogenins', Journal of the American Chemical Society, vol. 122, no. 21, pp. 5052-5064. https://doi.org/10.1021/ja994134s
Block, Eric ; Birringer, Marc ; Deorazio, Russell ; Fabian, Jürgen ; Glass, Richard S ; Guo, Chuangxing ; He, Chunhong ; Lorance, Edward ; Qian, Quangsheng ; Schroeder, T. Benjamin ; Shan, Zhixing ; Thiruvazhi, Mohan ; Wilson, George S. ; Zhang, Xing. / Synthesis, properties, oxidation, and electrochemistry of 1,2- dichalcogenins. In: Journal of the American Chemical Society. 2000 ; Vol. 122, No. 21. pp. 5052-5064.
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abstract = "Syntheses are presented of the 1,2-dichalcogenins: 1,2-dithiin, 1,2- diselenin, and 2-selenathiin, both substituted and unsubstituted. 1,2-Dithiin and 1,2-diselenin are prepared by reaction of PhCH2XNa (X = S or Se) with 1,4-bis(trimethylsilyl)-1,3-butadiyne followed by reductive cleavage and oxidation. 2-Selenathiin is similarly prepared using a mixture of PhCH2SeNa and PhCH2SNa. Reaction of titanacyclopentadienes with (SCN)2 or (SeCN)2 followed by bis(thiocyanate) or bis(selenocyanate) cyclization affords substituted 1,2-dithiins or 1,2-diselenins, respectively. With S2Cl2, 1,2- dithiins are directly formed from titanacyclopentadienes. Oxidation of 1,2- dithiins and 1,2-diselenins gives the corresponding 1-oxide and, with 1,2- dithiins and excess oxidant, 1,1-dioxides; oxidation of 2-selenathiin gives the 2-oxide. Electrochemical oxidation of 1,2-dichalcogenins, which have a twisted geometry, affords planar radical cations by an EC mechanism. One- electron AlCl3 oxidation of 3,6-diphenyl-1,2-dithiin gives the corresponding radical cation, characterized by EPR spectroscopy. Theoretical calculations result in a flattened structure for the 1,2-dithiin radical cation and a fully planar structure for the 1,2-diselenin radical cation. The 77Se NMR chemical shifts of 1,2-diselenin are characteristically high-field-shifted with respect to open chain diselenides in good agreement with results of GIAO-DFT calculations based on MP2 and DFT optimum geometries.",
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AU - Block, Eric

AU - Birringer, Marc

AU - Deorazio, Russell

AU - Fabian, Jürgen

AU - Glass, Richard S

AU - Guo, Chuangxing

AU - He, Chunhong

AU - Lorance, Edward

AU - Qian, Quangsheng

AU - Schroeder, T. Benjamin

AU - Shan, Zhixing

AU - Thiruvazhi, Mohan

AU - Wilson, George S.

AU - Zhang, Xing

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N2 - Syntheses are presented of the 1,2-dichalcogenins: 1,2-dithiin, 1,2- diselenin, and 2-selenathiin, both substituted and unsubstituted. 1,2-Dithiin and 1,2-diselenin are prepared by reaction of PhCH2XNa (X = S or Se) with 1,4-bis(trimethylsilyl)-1,3-butadiyne followed by reductive cleavage and oxidation. 2-Selenathiin is similarly prepared using a mixture of PhCH2SeNa and PhCH2SNa. Reaction of titanacyclopentadienes with (SCN)2 or (SeCN)2 followed by bis(thiocyanate) or bis(selenocyanate) cyclization affords substituted 1,2-dithiins or 1,2-diselenins, respectively. With S2Cl2, 1,2- dithiins are directly formed from titanacyclopentadienes. Oxidation of 1,2- dithiins and 1,2-diselenins gives the corresponding 1-oxide and, with 1,2- dithiins and excess oxidant, 1,1-dioxides; oxidation of 2-selenathiin gives the 2-oxide. Electrochemical oxidation of 1,2-dichalcogenins, which have a twisted geometry, affords planar radical cations by an EC mechanism. One- electron AlCl3 oxidation of 3,6-diphenyl-1,2-dithiin gives the corresponding radical cation, characterized by EPR spectroscopy. Theoretical calculations result in a flattened structure for the 1,2-dithiin radical cation and a fully planar structure for the 1,2-diselenin radical cation. The 77Se NMR chemical shifts of 1,2-diselenin are characteristically high-field-shifted with respect to open chain diselenides in good agreement with results of GIAO-DFT calculations based on MP2 and DFT optimum geometries.

AB - Syntheses are presented of the 1,2-dichalcogenins: 1,2-dithiin, 1,2- diselenin, and 2-selenathiin, both substituted and unsubstituted. 1,2-Dithiin and 1,2-diselenin are prepared by reaction of PhCH2XNa (X = S or Se) with 1,4-bis(trimethylsilyl)-1,3-butadiyne followed by reductive cleavage and oxidation. 2-Selenathiin is similarly prepared using a mixture of PhCH2SeNa and PhCH2SNa. Reaction of titanacyclopentadienes with (SCN)2 or (SeCN)2 followed by bis(thiocyanate) or bis(selenocyanate) cyclization affords substituted 1,2-dithiins or 1,2-diselenins, respectively. With S2Cl2, 1,2- dithiins are directly formed from titanacyclopentadienes. Oxidation of 1,2- dithiins and 1,2-diselenins gives the corresponding 1-oxide and, with 1,2- dithiins and excess oxidant, 1,1-dioxides; oxidation of 2-selenathiin gives the 2-oxide. Electrochemical oxidation of 1,2-dichalcogenins, which have a twisted geometry, affords planar radical cations by an EC mechanism. One- electron AlCl3 oxidation of 3,6-diphenyl-1,2-dithiin gives the corresponding radical cation, characterized by EPR spectroscopy. Theoretical calculations result in a flattened structure for the 1,2-dithiin radical cation and a fully planar structure for the 1,2-diselenin radical cation. The 77Se NMR chemical shifts of 1,2-diselenin are characteristically high-field-shifted with respect to open chain diselenides in good agreement with results of GIAO-DFT calculations based on MP2 and DFT optimum geometries.

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