Darstellung und Kristallstruktur von (PPh₃)₃Ag₂WS₄, einem neuartigen Dreikern-Komplex mit tetraedrisch und trigonal planar koordinierten Ag-Atomen / Preparation and Crystal Structure of (PPh₃)₃Ag₂WS₄, a Novel Trinuclear Complex with Tetrahedral and Trigonal Planar Coordination of the Ag Atoms

Abstract

<jats:p>The title compound was prepared by reaction of AgNO<jats:sub>3</jats:sub>, P(C<jats:sub>6</jats:sub>H<jats:sub>5</jats:sub>)<jats:sub>3</jats:sub> and (NH<jats:sub>4</jats:sub>)<jats:sub>2</jats:sub>WS<jats:sub>4</jats:sub> in a dichloromethane/water system. The crystal structure was determined from single crystal X-ray diffraction data (monoclinic, space group P2<jats:sub>1</jats:sub>/c, with a = 1811,1(2), b = 1735.6(2), c = 1779,7(2) pm, β = 95,02(1)°, V = 5572,7 · 10<jats:sup>6</jats:sup> pm<jats:sup>3</jats:sup>, Z = 4). The compound contains a tetradentate WS<jats:sub>4</jats:sub><jats:sup>2-</jats:sup> ligand and two silver atoms, having a tetrahedral and trigonal planar coordination.</jats:p>

Structure of Ag(CHPh3)(1-Me-CB11F11). Trigonal-Planar Ag(Arene)3+ Cations, Polymeric {Ag(CHPh3)+}∞ Triangular-Net Layers, and Partially Aligned Interstitial Carborane Anions in a Polar Crystal

“…Given the lack of evidence for significant π back-bonding in silver(I) carbonyls, one can safely assume that there cannot be significant π back-bonding in silver(I) arene complexes, at least not in Ag(arene) x + complexes with no other σ-donor ligands (this conclusion has been reached by others). The trigonal-planar coordination geometry is not common for silver(I). − The structural parameters that support the trigonal-planar assignment (as opposed to the trigonal−pyramidal alternative), are as follows. The midpoints of the three coordinated arene C−C bonds form a nearly equilateral triangle with sides of 4.0, 4.1, and 4.4 Å and angles of 56°, 59°, and 65°, and the Ag + ion is displaced only 0.15 Å from the plane of this triangle (significantly, the Ag + ion is displaced away from F6 with respect to this plane, not toward it).…”

The Heterobimetallic Polymeric Zigzag Chain [(W4S16Ag4)4-]n Derived from the Linear Chain [(WS4Ag)-]n: Synthesis, Characterization, and Structure of [W4S16Ag4·2Ca(DMSO)6]n (DMSO = Dimethyl Sulfoxide)

“…The thiometalates, such as tetrathiotungstate and tetrathiomolybdate, have been extensively used in the synthesis of transition metal sulfides . For the tungsten(molybdenum)−silver−sulfur system, many discrete complexes have been obtained, such as [(PPh 3 ) 2 AgS 2 MS 2 Ag(PPh 3 )·0.8CH 2 Cl 2 ] (linear), [Et 4 N][(PPh 3 ) 2 AgS 3 MOCu(CN)](butterfly-type), [{Ag(Ph 3 P)} 3 MS 4 {S 2 P(OEt) 2 }](cubane-like), [(PPh 3 ) 4 Ag 4 W 2 S 8 ](cage), [Bu 4 N] 2 [M 2 Ag 3 (μ 3 -S) 2 (μ-S) 4 S 2 Et 2 dtc], and [Ag 6 S 6 M 2 (SCMe 3 ) 2 (O) 2 (PPh 3 ) 4 ] (double-cubane-like) (M = Mo, W), but polymeric complexes of this kind are fewer, with their general polymeric configuration being linear chain, e.g. [PPh 4 ·AgMoS 4 ] n , [AgMS 4 ·4-MePyH] n , and [tmenH 2 ·W 2 Ag 2 S 8 ·tmen·H 2 O] n (M = Mo, W; tmen = N , N , N‘ , N‘ -tetramethylethylenediamine).…”

Electronic Structures and Nonlinear Optical Properties of Trinuclear Transition Metal Clusters M−(μ-S)−M‘ (M = Mo, W; M‘ = Cu, Ag, Au)

“…In this paper, six molecular clusters in the Mo(W)−S(Se)−Cu(Ag, Au) series have been modeled and studied. They include (a) MoS 4 Cu(PPh 3 ) 2 Cu(PPh 3 ), (b) MoS 4 Ag(PPh 3 ) 2 Ag(PPh 3 ), (c) WS 4 Cu(PPh 3 ) 2 Cu(PPh 3 ), (d) WS 4 Ag(PPh 3 ) 2 Ag(PPh 3 ), (e) MoS 4 Au(PPh 3 )Au(PPh 3 ), and (f) WS 4 Au(PPh 3 )Au(PPh 3 ) …”

“…The isotropic scalar values for µ, R, β, and γ averaged from their tensor components are defined as 30 In this paper, six molecular clusters in the Mo(W)-S(Se)-Cu-(Ag, Au) series have been modeled and studied. They include (a) MoS 4 Cu(PPh 3 ) 2 Cu(PPh 3 ), 31 (b) MoS 4 Ag(PPh 3 ) 2 Ag(PPh 3 ), 32 (c) WS 4 Cu(PPh 3 ) 2 Cu(PPh 3 ), 32 (d) WS 4 Ag(PPh 3 ) 2 Ag(PPh 3 ), 33 (e) MoS 4 -Au(PPh 3 )Au(PPh 3 ), 34 and (f) WS 4 Au(PPh 3 )Au(PPh 3 ). 35 A summary of the crystalline structure data of these clusters is given in Table 1.…”