Über die Reaktivität von [(CH3)2N]6W2 (W≡W) gegenüber CS2/S8 und CS2/Se8. Röntgenstrukturanalyse von [(CH3)2NCS2]2W(S)(S2) / Reactivity of [(CH3)2N]6W2 (W≡W) Towards CS2/S8 and CS2/Se8. X-Ray Structure Analysis of [(CH3)2NCS2]2W(S)(S2)

Abstract

Abstract In this paper we report two improved preparation methods for [(CH3)2N]6W2 (W≡W) (1), one starting from WCl4 (yield 51%), and a second one starting from W2C16(THF)4 (ca. 60% yield). We have studied the reactions of 1 with different nucleophiles, among them triphenylalkylidenphosphoranes (like Ph3P=CH2 and Ph3P=CHPh·LiCl; Ph = phenyl), sulfur and CS2 . 1 reacts with S8 and CS2 in hexane to yield the two new compounds (Me2NCS2)2WS(S2) (4) and W(CS2H)(Me2NCS2)2 (5), both containing dithiocarbamato ligands formed by insertion of CS2 into the W-N bond. The two mononuclear compounds were characterized spectroscopically, in the case of 4 an X-ray diffraction structure analysis was performed. The reaction of 1 with Se and CS2 , leads to the compounds 4, (Me2NCS2)2W2S4 (6) and [(Me2N)2C]CS2 (7), which were also characterized spectroscopically. No Se-containing compounds could be isolated. 4 crystallizes monoclinically, C5 2h-P21/n, with a = 648.6(3), b = 1346.7(6) and c = 1745.9(7) pm, β = 91.85(3)°, V = 1524x106 pm3 , Z = 4. The structure of the seven-coordinate tungsten compound is discussed and compared to complexes with similar ligands and geometry.