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

The metallacycles [Cl 3 MS 2 N 3 ] 2 (M = Mo, W) 1a and 2a have been obtained from reactions of S 4 N 4 with Mo 2 Cl 10 and WCl 6 , respectively, and from S 3 N 3 Cl 3 with the hexacarbonyls M(CO) 6 . The adducts Cl 3 MS 2 N 3 · CH 3 CN 1b and 2b are formed with acetonitrile, and the salts [Ph 4 As + ][Cl 4 MS 2 N 3 - ] 1c and 2c with addition of Ph 4 AsCl. Reactions of Mo 2 Cl 10 and WCl 6 , respectively, with related S -N com pounds lead predominantly to 1a and 2a; Mo 2 Cl 10 reacts with S 3 N 2 Cl 2 to give 1a , and with [Me 3 SiN] 2 S to give [Cl 3 MoN] x , while WCl 6 yields Cl 4 WNSCl with S 3 N 2 Cl 2 , and 2a with [Me 3 SiN] 2 S. [Cl 3 MoN ] x does not react with S 4 N 4 , but [Cl 3 WN] x forms 2a. Reactions of VCl 4 and VOCl 3 with [Me 3 SiN] 2 S give [Cl 2 V S 2 N 3 ] x , 3. 2c has also been obtained by the reaction of [Ph 4 As + ][Cl 5 WNSCL - ] with [Me 3 SiN] 2 S. The oxidation states of the metal atoms are +6 for 1a-c and 2a-c, and +5 for 3, respectively; as determined by 51 V and 95 Mo 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.