Monika Kustos

SULFUR COMPOUNDS 1411: SYSTEMATIC BUILD-UP OF ORGANIC POLYSULFANES - SYNTHESIS AND SPECTRA OF THE CYCLIC HEPTA- AND OCTASULFANES OF NORBORNANE, C7H10S7 AND C7H10S8

Abstract The cyclic polysulfanes exo-3,4,5,6,7,8,9-heptathiatricyclo[9.2. 1.02, 10]tetradecane (C7H10S7) and exo- 3,4,5,6,7,8,9,10-octathiatricyclo[10.2.1.02.11]-pentadecane (C7H10S3) have been prepared from the corresponding trisulfane C7H10S3 by chlorination resulting in the two sulfenylchlorides C7H10(SCI)2 and C7H10(SCI) (S2CI) which react with (C5H5)2TiS5 to yield the title compounds in good yields. Similarly, C7H10S5CI2 was obtained from C7H10S5 and Cl2 and yielded C7H10S10 on treatment with (C5H5)2TiS5. The hepta- and octasulfanes form pale-yellow microcrystals which have been characterized by UV, mass, Raman, and 1H NMR spectroscopy. The retention time of C7H10Sn molecules in reversed-phase HPLC is a function of the number of sulfur atoms (n = 3… 12).

Crystal and Molecular Structures of the Sulfur-Rich Organic Polysulfanes Heptathiacyclononane (C2H4S7) and Bis(triphenylmethyl)pentaand hexasulfane

Determination of the first structure of a chain-like polysulfane with five sulfur atoms in the chain has been attempted. Bis(triphenylmethyl)pentasulfane forms monoclinic crystals containing disordered solvent molecules preventing an accurate solution of the structure. The (Ph3C)2S5 molecules consist of a helical C–S–S–S–S–S–C backbone (all torsion angles of same sign) and triphenylmethyl groups of normal conformation. The analogous (Ph3C)2S6 forms triclinic crystals; the molecular conformation of the C–S6–C chains is not helical, but the motif of torsion angles is + + – – +. In both compounds the C– S bonds are considerably longer (191 pm) than comparable C–S single bonds as in cyclo-C2H4S7. The latter forms monoclinic crystals consisting of ring molecules of C1 symmetry which can formally be derived from the crown-shaped S8 ring by substituting one sulfur atom by a C2H4 group of approximate C2h symmetry.

Synthesis and Structure of Bis[di(methylcyclopentadienyl)chloro-titanium]trisulfide [(Cp′2ClTi)2S3] - a Reagent for Trisulfide Ligand Transfer Reactions [1]

The dinuclear metallacycle of [Cp′2Ti(μ-S2)2TiCp′2.] reacts with phosgene or thiophosgene to give [(Cp′2CITi)2S3] which has been characterized by 1H and 13C NMR spectra as well as by an X-ray structure analysis. The trisulfido complex contains a helical TiSSSTi unit and may serve as an S3 transfer reagent in reactions with SCl-functional compounds

The Utilization of Titanocene Polysulfide Complexes for the Synthesis of Organic Polysulfanes1

Abstract Titanocene pentasulfide reacts with Ph3CCl and CCl3SCl to give (Ph3C)2S5 and (CCl3)2S7, respectively, the molecular structures of which show helical CSnC backbones. (Ph3C)2S6 and (CN)2S9 possess non-helical structures. C2H4(SCl)2, C6H4(SCl)2, C6H4(SSCl)2 and CH3C6H3(SCl)2 react with Cp2TiS5 to give the corresponding sulfur-rich heterocycles with up to nine sulfur atoms. Dicyclopentadiene trisulfane is used to prepare the dicyclopentadiene tetra-, penta-, hexa- and octa-sulfanes by (a) derivatization to SCl or SH compounds followed by sulfur transfer reactions using Cp2TiS5, (Cp′2ClTi)2S3 or S2Cl2 as reagents. Several cyclic, bicyclic and tricyclic organosulfur heterocycles are obtained from Cp4Ti2C2S4 or from Cp2TiS2C3H6 by reactions with SCl2, S2Cl2, C2H4(SCl)2, COCl2 or C6H4(SCl)2.

Synthesis and vibrational spectra of new bis(alkoxysulfane)-dichloropalladium(II) complexes and X-ray structural analysis of [PdCl2{S(OPri)2}2]

Reactions of L =(PriO)2S, (PrnO)2S, (MeO)(C4H8NO)S (C4H8NO = morpholino), (MeO)(C5H10N)S (C5H10N = piperidino) or (MeO)PhS with [PdCl2(NCPh)2] in toluene gave five complexes of type [PdCl2L2](yields 40–79%). An X-ray structural analysis of the air-stable, monoclinic crystals of [PdCl2{S(OPri)2}2] showed the sulfur atoms to be cis-planar co-ordinated. The two co-ordinated dialkoxysulfane ligands are rotational isomers with differing SO torsional angles (+79 and 84° for ligand 1, –106 and +82° for 2). The S–O bond lengths are in the range 1.586–1.611 A. The infrared and Raman spectra of the five [PdCl2L2] complexes demonstrate that the rule of mutual exclusion is not obeyed, indicating a cis rather than a trans co-ordination in each case.

Methyl 3-(1,3-benzothiazol-2-yldithio)-propanoate, C11H11NO2S3

The benzothiazole unit is similar to those found in other derivatives, e.g. bis(1,3-benzothiazol-2-yl) disulfide [Zingaro & Meyers (1980). Cryst. Struct. Commun. 9, 1167-1172] or 2-methylthio-1,3-benzothiazole [Wheatley (1962). J. Chem. Soc. p. 3636]. The S atoms of the disulfide group and the condensed ring system are nearly coplanar (torsion angle τ NCSS +9.3 o ). The overall conformation of the title compound is almost linear

X-Ray Structural Analysis and Vibrational Spectra of Sodium Cysteine-S-sulfonate, +H3NCH(COO-)CH2S2O3Na • 3/2H2O [1]

The title compound crystallizes orthorhombically (space group C 2221) with a = 797.0, b = 870.3 and c = 2739.0 pm. The anions are zwitterions which are heavily involved in intra- and intermolecular NH •••O and OH•••O hydrogen bonding. The two types of sodium cations are coordinated by six oxygen atoms each of which belongs to either SO3 groups (Na 2) or water molecules and SO3 groups (Na1). A second type of water molecules is not coordinated to the cations. The SS bond length is 208.2 pm. Infrared and Raman spectra of the title compound are reported and tentatively assigned. The SS stretching vibration is observed at 409 cm-1.