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  • 1
    ISSN: 0009-2940
    Keywords: Titanocene complexes ; S ligands ; Organic polysulfanes ; Ligand transfer reactions ; Sulfur heterocycles ; Chalcogens ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2057-2061 
    ISSN: 1434-1948
    Keywords: Sulfur ; Sulfanes ; Acidity ; Ab initio MO calculations ; Hyperconjugation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase acidities ΔGacid(298 K) of the sulfanes H2Sn (n = 1-4) have been calculated by ab initio molecular orbital theory using the G2 and G2(MP2) methods, which were applied to the geometries of lowest energy. The results show that the higher sulfanes are surprisingly strong proton donors. The acidities (in kJ mol-1) are as follows: H2S (1444), H2S2 (1406), H2S3 (1370), H2S4 (1347). The latter three values may be compared to those of other strong Brønsted acids like gaseous HNO2 (1396), HCl (1371), and HBr (1332). The monoanions HSn- exhibit an interesting bond length distribution as a consequence of the charge delocalization by hyperconjugation, which in turn may be responsible for the high acidities of the sulfanes.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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