[Ni₂(SC₄H₉)₆]^2-, ein neuartiger zweikerniger Nickel-Thiolato-Komplex mit kantenverknüpften NiS₄-Tetraedern und [Ni(SC₆H₄SiMe₃)₄]^2-, ein strukturchemisch verwandtes einkerniges Komplexion / [Ni₂(SC₄H₉)₆]^2-, a Novel Binuclear Nickel-Thiolat Complex with NiS₄ Tetrahedra Sharing Edges and [Ni(SC₆H₄SiMe₃)₄]^2-, a Structurally Related Mononuclear Complex Ion

Abstract

Reaction of nickel(II) chloride with sodium or potassium tert-butane thiolate in acetonitrile affords the isotypical compounds [Ni 2 (StC 4 H 9 ) 6 ]Na 2 ·4MeCN (1) and [Ni 2 (StC 4 H 9 ) 6 ]K 2 · 4MeCN (2), respectively. Crystal data: 1: a = 9.859(3), b = 11.877(3), c = 19.675(5) Å , β = 96.11(2)°, space group P2 1 /n, Z = 2:2: a = 9.854(2), b = 11.915(3), c = 20.558(5) Å , β = 99.62(2)°, space group P2 1 /n, Z = 2. The structures were refined to R = 0.0599 (1) and 0.0562 (2), respectively. Both compounds contain the complex ion [Ni 2 (SrC 4 H 9 ) 6 ] 2- (3), which is not only the first example of a tetrahedral nickel complex with alkane thiolate ligands, but also the first polynuclear nickel complex containing tetrahedral NiS 4 -units sharing a common edge. Reaction of nickel(II) chloride and sodium (2-trimethylsilyl)thiophenolate in acetonitrile leads to [Ni(SC 6 H 4 SiMe 3 ) 4 ] 2- (5) with tetrahedral stereochemistry. The mononuclear complex ion is isolated aso [Ph 4 P] 2 [Ni(SC 6 H 4 SiMe 3 ) 4 ] · 5MeCN (4) with a = 13.771(2), b = 14.163(2), c = 25.873(4) Å , a = 77.44(1), β = 75.13(1), γ = 72.46(1)°, space group P1̅ and Z = 2. The final refinement converged to R = 0.0445.