Darstellung und Eigenschaften von Cyclo-1λ6-metalla-3,5-ditha-2,4,6-triazenen / Synthesis and Properties of Cyclo-1λ6-metalla-3,5-dithia-2,4,6-triazenes

Abstract

The metallacycles [Cl3MS2N3]2 (M = Mo, W) 1a and 2a have been obtained from reactions of S4N4 with Mo2Cl10 and WCl6, respectively, and from S3N3Cl3 with the hexacarbonyls M(CO)6. The adducts Cl3MS2N3 · CH3CN 1b and 2b are formed with acetonitrile, and the salts [Ph4As+][Cl4MS2N3 -] 1c and 2c with addition of Ph4AsCl. Reactions of Mo2Cl10 and WCl6, respectively, with related S -N com pounds lead predominantly to 1a and 2a; Mo2Cl10 reacts with S3N2Cl2 to give 1a , and with [Me3SiN]2S to give [Cl3MoN]x, while WCl6 yields Cl4WNSCl with S3N2Cl2, and 2a with [Me3SiN]2S. [Cl3MoN ]x does not react with S4N4, but [Cl3WN]x forms 2a. Reactions of VCl4 and VOCl3 with [Me3SiN]2S give [Cl2V S2N3]x, 3. 2c has also been obtained by the reaction of [Ph4As+][Cl5WNSCL-] with [Me3SiN]2S. The oxidation states of the metal atoms are +6 for 1a-c and 2a-c, and +5 for 3, respectively; as determined by 51V and 95Mo NMR spectroscopy and magnetic susceptibility measurements. The UV/VIS spectra of 1b , 1c , 2b, c and 3 are discussed. The electrical conductivity of 3 is reported.