Zur Chemie der Chlorthionitrenkomplexe des Rheniums Die Kristallstruktur von [N(SCl)2]⊕ [Re2Cl9]⊖

Chemistry of Chlorothionitrene Complexes of Rhenium. Crystal Structure of N(SCl)₂]⊕ Re₂Cl₉]? By reaction of S₃N₂Cl₂ with ReCl₅ the chlorothionitrene complex ReCl₃(NSCl)₂]₂ is obtained in good yield; it has a dimer structure with chloro bridges. By the same reaction in POCl₃ solution the solvate ReCl₃(NSCl)₂OPCl₃] is obtained. Instead, when a molar ratio of ReCl₅ and S₃N₂Cl₂ of 2:1 is taken, the product is N(SCl)₂]Re₂Cl₉]. ReCl₄(NSCl)OPCl₃] and excess PPh₃ react to give the nitrido complex ReNCl₂(PPh₃)₂]. The crystal structure of N(SCl)₂]Re₂Cl₉] was determined and refined with X-ray diffraction data (1021 independent reflexions, R = 0.031). It crystalizes in the space group C2/c with four formula units per unit cell (a = 1197, b = 1288, c = 1144 pm, ß = 107.83°). The N(SCl)₂]⊕ cations have exactly C₂ and approximately C_2v symmetry; the NS bond lengths of 162 pm and the bond angles SNS (133.6°) and NSCl (117.6°) deviate considerably from the values of known N(SCl)₂]⊕ structures. The Re₂Cl₉]? anion consists of two face sharing octahedra and has a Re—Re distance of 270 pm. I. r. spectra of all compounds are reported and discussed.