Synthesis and reactions of binary metal sulfides. Structural characterization of the [(S4)2Zn]2-, [(S4)2Ni]2-, [(S5)Mn(S6)]2-, and [(CS4)2Ni]2- anions

D. Coucouvanis, P. R. Patil, Mercouri G Kanatzidis, B. Detering, N. C. Baenziger

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Abstract

A general procedure for the synthesis of the polysulfido, [M(Sx)2]2-, complexes (M = Zn, x = 4-6; M = Cd, x = 5; M = Ni, x = 4; M = Mn, x = 5, 6) is described. These complexes and the mixed thiophenolate polysulfido complexes, [M(SPh)2(Sx)2]2- (M = Zn, x = 4, 5; M = Cd, x = 5), are obtained by the oxidation of all or two of the thiophenolate ligands in the [M(SPh)4]2- complexes by dibenzyl trisulfide with the concomitant generation of the polysulfide dianions. The diamagnetic [Ni(S4)2]2- and high-spin [Mn(Sx)2]2- complexes react readily with CS2 to give the corresponding perthiocarbonate complexes [Ni(CS4)2]2-, [Mn(CS4)2]2-, and [Mn(S6)(CS4)]2-. The structures of the tetraethylammonium salts of [Zn(S4)2]2- (I) and [Ni(S4)2]2- (II) and of the tetraphenylphosphonium salts of [Ni(CS4)2]2- (III) and [MnS11]2- (IV) have been determined by X-ray crystallography. Lattice parameters and space group information are as follows: for I, a = 12.410 (3) Å, b = 16.350 (1) Å, c = 13.906 (2) Å, α = 90.00°, β = 95.73 (1)°, γ = 90.00°, monoclinic, P21/c (Z = 4); for II, a = 10.475 (2) Å, b = 10.452 (2) Å, c = 12.738 (2) Å, α = β = γ = 90.00°, orthorhombic, Pnn2 (Z = 2); for III, a = 9.231 (3) Å, b = 10.156 (3) Å, c = 13.694 (4) Å, α = 82.48 (1)°, β = 72.12 (1)°, γ = 85.51 (1)°, triclinic, P1 (Z = 1); for IV, a = 23.266 (5) Å, b = 20.390 (3) Å, c = 23.894 (5) Å, α = 90.00°, β = 118.03 (1)°, γ = 90.00°, monoclinic, P21/n (Z = 8). Diffraction data (Mo Kα radiation, 2θmax = 50, 45, 40, 45, respectively, for I-IV) were collected by either a Picker FACS-I (I) or a Nicolet P3F automatic diffractometer (II-IV). The structures were solved and refined by direct methods and full-matrix least-squares procedures to R values of 0.062, 0.041, 0.030, and 0.121, respectively, for I-IV from 2481, 831, 1971, and 6495 reflections on 244, 149, 280 and 277 variables, respectively, for I-IV. The anion in I contains the Zn tetrahedrally coordinated by two bidentate S42- chelates, Zn-S = 2.351 Å. In II the coordination of the two S42- chelates around the Ni(II) ion gives a square-planar complex, Ni-S = 2.179 Å. The anion in III is planar, and in the two bidentate CS42- chelates the C=S groups are located trans to each other, Ni-S = 2.170 Å. The [(S5)Mn(S6)]2- and [(S5)Mn(S5)]2- anions both occupy the anion sites in IV where the Mn(II) is tetrahedrally coordinated by the Sx2- chelates Mn-S = 2.425 Å. A discussion of S-S bonding in the S42- and CS42- chelates is presented.

Original languageEnglish
Pages (from-to)24-31
Number of pages8
JournalInorganic Chemistry
Volume24
Issue number1
Publication statusPublished - 1985

ASJC Scopus subject areas

  • Inorganic Chemistry

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