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New syntheses of [Fe2S2Cl4]2" (1) and [Fe2OCl6]2" (2) and terminal oxo/sulfido ligand substitution reactions have been devised with use of the reagents (Me3Si)2S (3), NaSSiMe3 (4), and NaOSiMe3 (5) in acetonitrile solutions. The preparation of 4 is described. Reactions of (Et4N) [FeCl4] with equimolar quantities of 3, 4, and 5 in acetonitrile afford the Et4N+ salts of 1 (76%, 77%) and 2 (66%), respectively, in good yields. In THF (Et4N)2(l) was isolated in essentially quantitative yield from a reaction using 3. Equimolar amounts of 2 and 3 give partial conversion to 1 in a bridge oxo/sulfido substitution reaction; a competing reaction is that of product Me3SiCl with 2 to form [FeCl4]~. The chelate complex VO(acen) reacts with excess 3 to give a quantitative in situ yield of VS(acen). On a preparative scale a 79% yield was obtained. Similarly, NbO(S2CNEt2)3 was converted to yellow NbS(S2CNEt2)3 (vNbs = 493 cm"1) in 52% isolated yield. These syntheses of 1 and 2 in particular offer advantages over previous methods. The results presented suggest that silylsulfide reagents may have extended utility in effecting bridging and terminal oxo/sulfido transformations. Physical Measurements. Electronic spectra were recorded on a Cary Model 219 spectrophotometer.

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Die Titelkomplexe (II) werden durch Oxidation der Bis‐[μ‐thio]‐dichloroferrat(II)‐dithiomolybdat(wolframat)(VI)‐Komplexe (I) mit Fe‐trichloridhydrat oder durch direkte Synthese aus [NH4)2(MoS4], FeCl2 · H2O und Ph4PCl synthetisiert.

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