SYNTHESIS OF THE DICYCLOPENTADIENE POLYSULFANES C10H12SN WITH N=4-8 USING TITANOCENE POLYSULFIDE COMPLEXES AS SULFUR-TRANSFER REAGENTS

The dicyclopentadiene polysulfanes C10H12Sn (n = 4-8) are prepared usi ng the sulfur-transfer reagents Cp(2)TiS(5) and (Cp'2TiCl)(2)S-3 (Cp' = eta(5)-C5H4CH3) Or S2Cl2 in combination with novel SC1 derivatives o f dicyclopentadiene of type C10H12(SnCl)(SmCl) (n, m = 1, 2) or the di thiol of dicyclopentadiene, respectively. Dicyclopentadienedithiol C10 H12(SH)(2) reacts with SO2Cl2 to give the bis(sulfenyl chloride) C10H1 2(SCl)(2) and with an excess of SCl2 it yields the bis(chlorodisulfane ) C10H12(S2Cl)(2). The mixed sulfenyl chloride C10H12(SCl)(S2Cl) was o btained from C10H12S3 by treatment with SO2Cl2 C10H12(SH)(2) and S2Cl2 give the novel C10H12S4 while C10H12S5 was obtained from C10H12(SCl)( 2) and (Cp'2TiCl)(2)S-3. The latter complex reacts with C10H12(SCl)(S2 Cl) to give C10H12S6 The formation of C10H12S7 from C10H12(SCl)(2) and Cp(2)TiS(5) was demonstrated by HPLC. The reaction of C10H12(SCl)(S2C l) with Cp(2)TiS(5) afforded C10H12S8. RP-HPLC is a suitable analytica l method to determine the number of sulfur atoms ns in C10H12Sn specie s since the retention time systematically increases with increasing It s. The H-1 NMR spectra of C10H12Sn, are different enough to allow the detection of these species in mixtures but in addition to the inductiv e effect of the varying number of sulfur atoms the conformation of the C2Sn unit exercises an important influence on the chemical shift of t he protons.