| Abstract: | Molybdenum and Tungsten Complexes with MNS Sequences. Crystal Structures of MoCl3(N3S2)(1,4‐dioxane)2] and Mo2Cl2(μ‐NSN)2(μ‐O)(NCMe3)(OCMe3)2]2 The cyclo‐thiazeno complexes Cl3MNSNSN]2 of molybdenum and tungsten react with 1,4‐dioxane in dichloromethane suspension to give the binuclear donor‐acceptor complexes μ‐(1,4‐dioxane){MCl3(N3S2)}2] which are characterized by IR spectroscopy. With excess 1,4‐dioxane the molybdenum compound forms the complex MoCl3(N3S2)(1,4‐dioxane)2] in which, according to the crystal structure determination, one of the dioxane molecules coordinates at the molybdenum atom, the other one at one of the sulfur atoms of the cyclo‐thiazeno ring. The μ‐(NSN2–) complex Mo2Cl2(μ‐NSN)2(μ‐O)(NCMe3)(OCMe3)2]2 has been obtained by the reaction of MoN(OCMe3)3] with trithiazyle chloride in carbontetrachloride solution. According to the crystal structure determination this compound forms centrosymmetric dimeric molecules via two of the nitrogen atoms of two of the μ‐(NSN) groups to give a Mo2N2 fourmembered ring. MoCl3(N3S2)(1,4‐dioxane)2]: Space group P21/c, Z = 4, lattice dimensions at –70 °C: a = 1522.9(2); b = 990.3(1); c = 1161.7(1) pm; β = 106.31(1)°, R1 = 0.0317. Mo2Cl2(μ‐NSN)2(μ‐O)(NCMe3)(OCMe3)2]2 · 4 CCl4: Space group P21/c, Z = 2, lattice dimensions at –83 °C: a = 1216.7(1); b = 2193.1(2); c = 1321.8(1) pm; β = 98.23(1)°; R1 = 0.0507. |
