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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 ...

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.

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).