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Treatment of Cp2Ti(CO)2 (3) with the di- and polysulfanes 1,2,4-(CH2)2S3, C4S6 (9), C,7H10S3 (11), 1,2,4,6-(CH2)3S4 (16), C6H10S6(19), and S6 affords the titanocene chelate complexes Cp2TiS3(CH2)2 (8), (Cp2Ti)2C4S6 (10), Cp2TiS3C7H10 (13), Cp2TiS2C7H10 (14), Cp2TiS4(CH2)3 (17), Cp,2TiS6C6H6H10 (20), and Cp2TiS8 (23). 14 is also obtained from Cp2TiCl2 (1) and the geminal dithiol of norbornene. The analogous reaction with the dithiol of dicyclopentadiene yields Cp2TiS2C10H12 (15). In ligand transfer reactions, 8 reacts with SCl2 to give 1,2,3,5-tetrathiane (25), 10 provides 9 on reaction with Cl2, 13 when treated with S2Cl2 affords C7H10S5 (12), 15 reacts with S2Cl2Cl2 to give C10H12S4. 17 and SCl2 yield 1,2,3,5,7-pentathiepane (18), 20 is converted to C6H10S7 (22) on reaction with SCl2, and 23 yields S10 and 1,2,-C6H4(SCl)2, respectively. With phosgene, thiophosgene, and thionyl chloride, compound 15 yields the corresponding dithiocarbonate 26, the trithiocarbonate 27 and the trisulfane 2-oxide 28. The structure of 27 was determined by X-ray crystallography.

New dendrimers 3-[G‘1]−3-[G‘4] possessing from 6 to 48 N(CH2PPh2)2 terminal groups are described. The corresponding Pd, Pt, and Rh complexes [N(CH2PPh2)2MRR‘]y (y from 6 to 24; generations 1−3) [M ...

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

Bis(2-benzothiazolyl)tetrasulfane prepared from the mercaptane and S2Cl2 crystallizes in the monoclinic space group C2/c with a = 3513 pm, b = 577.28 pm, c = 800.0 pm, β = 98.74°, ρ = 1.64 g cm−3 (at 298 K). The molecules are of C2 symmetry with the geometrical parameters of the S4 backbone: dss = 202.7 (terminal) and 207.3 pm (central), αsss = 106.4°, τssss = 78.5°. The overall conformation is all-trans. Bis(4-chlorophenyl)tetrasulfane prepared from the mercaptane and diisopropoxydisulfane crystallizes in the monoclinic space group P21/a with a = 1237.7 pm, b = 748.4 pm, c = 1623.9 pm, β = 105.58°, ρ = 1.61 g cm−3 (at 298 K). The molecules occupy general positions but are approximately of C2 symmetry with dss = 203.6 (terminal), 206.7 (central) and 202.3 pm (terminal), αsss = 107.4° and 108.4°, τssss = 75.5° (all-trans conformation). The intermolecular interactions are of van der Waals type. Infrared, Raman, mass and NMR spectra (1H, 13C) are reported. Kristall- und Molekulstrukturen sowie Spektren zweier organischer Tetrasulfane R2S4 (R = 2-Benzothiazolyl und 4-Chlorphenyl) Bis(2-benzothiazolyl)tetrasulfan, hergestellt aus dem Mercaptan und S2Cl2, kristallisiert in der monoklinen Raumgruppe C2/c mit den im Abstract angegebenen Zelldimensionen. Die Molekule haben C2-Symmetrie; das S4-Gerust ist von all-trans-Konformation mit den Parametern dss = 202,7 (terminal) und 207,3 pm (zentral), αsss = 106,4° und τssss = 78,5°. Bis(4-chlorphenyl)tetrasulfan kristallisiert in der monoklinen Raumgruppe P21/a (s. Abstract). Die Molekule befinden sich in allgemeinen Lagen, sind aber naherungsweise von C2-Symmetrie und ebenfalls von all-trans-Konformation mit dss = 203,6 (terminal), 206,7 (zentral) und 202,3 pm (terminal), αsss = 107,4° und 108,4° sowie τssss = 75,5°. Die intermolekularen Wechselwirkungen sind vom van der Waals-Typ. Infrarot-, Raman-, Massen- und NMR-Spektren (1H, 13C) der Verbindungen werden mitgeteilt.

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.

S4(CN)2 crystallizes in the monoclinic space group P21/c with a = 885.7 pm, b = 794.2 pm, c = 1032.6 pm, β = 109.0° (at 173 K). The molecules occupy general sites but are of approximate C2 symmetry. The conformation of the molecules is all-trans with torsional angles CSSS = 74.6° and 81.7° and SSSS = 84.8°. The central SS bond (201.7 pm) is much shorter than the terminal SS bonds (av. 206.8 pm). There are no stronger than van-der-Waals type intermolecular interactions. Kristall- und Molekulstruktur von Dicyanotetrasulfan S4(CN)2 S4(CN)2 kristallisiert in der monoklinen Raumgruppe P21/c mit den im Abstract angegebenen Parametern. Die Molekule besetzen allgemeine Lagen, sind aber ungefahr von C2-Symmetrie. Die Konformation ist all-trans mit den Torsionswinkeln CSSS = 74,6° und 81,7° sowie SSSS = 84,8°. Die mittlere SS-Bindung (201,7 pm) ist viel kurzer als die auseren (Mittelwert 206,8 pm). Die intermolekularen Wechselwirkungen sind vom van-der-Waals-Typ.

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.

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.

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).

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

C 7 H 10 S 5 cristallise dans P2 1 /n avec a=10.167, b=11.092, c=10.278A, β=115.22°, Z=4; affinement jusqu'a R=0.0339. Les deux atomes S alpha sont tous les deux en position exo dans le derive pentathiepane du norbornane, obtenu a partir de la reaction du norbornene avec du soufre active

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.