Die Bildung von PPh4[WOCl4 · THF] und PPh4Cl · 4As4S3 aus W(CO)6 und PPh4[As2SCl5] sowie ihre Kristallstrukturen

Formation of PPh₄WOCl₄ · THF] and PPh₄Cl · 4As₄S₃ from W(CO)₆ and PPh₄As₂SCl₅] and their Crystal Structures When W(CO)₆ and PPh₄As₂SCl₅] are irradiated with UV light in tetrahydrofurane, PPh₄WOCl₄ · THF], PPh₄ Cl· 4As₄S₃ and PPh₄Cl₂H] are obtained. X-ray crystal structure determinations were performed. PPh₄WOCl₄ · THF], monoclinic, space group P2₁/c, Z = 4, a = 1207.5(2), b = 1003.7(2), c = 2642.0(5) pm, β = 114.71(1)°, R = 0.049% for 2824 reflexions; PPh₄⁺ and WOCl₄. THF]^? ions are present, the WOCl₄ group having the shape of a tetragonal Pyramid with a short W ? O bond (169 pm) and the THF molecule being weakly associated (W? O 236 pm). PPh₄Cl · 4AsS₃, tetragonal, I4₁/a, Z = 4, a = 1742.3(3), c = 1664.5(4) pm, R = 0.066% for 1350 reflexions; it consists of separate PPh₄⁺ and Cl^? ions and As₄S₃ molecules.