Preparation of Organic Polysulfanes R2Sn (n = 5, 7, 8, 9) from Sulfenyl Chlorides, RSCl, and Transition Metal Polysulfido Complexes

Autor: Vera Münchow, Karin Hassenberg, Joachim Pickardt, Ralf Steudel, Oliver Schumann
Rok vydání: 2000
Předmět:
Zdroj: European Journal of Inorganic Chemistry. 2000:921-928
ISSN: 1099-0682
1434-1948
DOI: 10.1002/(sici)1099-0682(200005)2000:5<921::aid-ejic921>3.0.co;2-2
Popis: The preparation of seven novel organic polysulfanes is reported. Bis(n-octyl)heptasulfane R2S71 is formed upon reaction of RSCl with [Cp2TiS5], while the corresponding nonasulfane R2S92 is obtained by reaction of RSSCl with [Cp2TiS5]. The bis(n-octyl)pentasulfane R2S53 is obtained from RSCl and [(Cp′2TiCl)2S3] by transfer of the S3 ligand at 20 °C. The new alkyl polysulfanes 1–3 have been obtained in quantitative yields. They are liquids at 20 °C, having freezing points below –50 °C, but do not form mesogenic phases. Reactions of [Cp2TiS5] with 2-naphthyl- and 4-chlorophenyl sulfenyl chloride furnish the corresponding heptasulfanes 4 and 5, respectively, which are solids at 20 °C. 1,2-Benzodisulfenyl chloride C6H4(SCl)2 reacts with [(Cp′2TiCl)2S3] to give the known 1,2,3,4,5-benzopentathiepin C6H4S56, with [Cp2TiS5] to give the novel 1,2,3,4,5,6,7-benzoheptathionin C6H4S77, and with [(TMEDA)ZnS6] to give the novel 1,2,3,4,5,6,7,8-benzooctathiecin C6H4S88. The cyclic polysulfanes 6–8 are solids at 20 °C and have been recovered in yields of 60–83%. The orthorhombic structure of 1,2-C6H4S7 has been investigated by single-crystal X-ray diffraction analysis. The molecules are found to be located at sites of Cs symmetry and the motif of the C2S7 heterocycle is +–+–+–+–, with the torsion angle of zero at the carbon–carbon bond. The three internuclear SS distances measure 205.0(1), 203.7(1), and 205.7(1) pm.
Databáze: OpenAIRE
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