Chemistry of chlorothionitrene complexes of rhenium

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, β = 107.830). The [N(SCl)2]+ cations have exactly C2 and approximately C/sub 2v/ summetry; the NS bond lengths of 162 pm and the bond angles SNS (133.60) and NSCl (117.60) 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. (author)