Darstellung,Mössbauer- und Schwingungsspektren der Komplexe [SnCl4F]⊖, [SnCl4(NCS)]⊖ und [SnCl4(NCS)2]2⊖

Preparation, Mössbauer and Vibrational Spectra of the Complexes [SnCl₄F]^?, [SnCl₄(NCS)]^?, and [SnCl₄(NCS)₂]^2? N(CH₂)₄F and N(CH₂)₄SCN react in liquid SO₂ with SnCl₄ yielding the adducts [N(CH₃)₄][SnCl₄F] (I), [N(CH₃)₄][SnCl₄(NCS)] (II) and [N(CH₃)₄]₂[SnCl₄(NCS)₂] (III).respectively. Mössbauer and vibrational spectra indicate for the anion of I a fluoro-bridged species, which is probably tetrameric like the isoelectronic SbCl₄F. For II dimeric moieties are proposed with bridging S-atoms, while [SnCl₄(NCS)₂]^2? has an octahedral structure with N-bonded isothiocyanate groups in the trans-positions.     

ChemInform Abstract: Electronic Structure Study of the [Ag—Ag]4‐, [Au—Au]4‐, and [Hg—Hg]2‐ Zintl Anions in the Intermetallic Compounds Yb3Ag2, Ca5Au4, and Ca3Hg2: Transition Metal Anions as p‐Metal Elements

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Structural features of Ag[AuF4] and Ag[AuF6] and the stuctural relationship of Ag[AgF4]2 and Au[AuF4]2 to Ag[AuF4]2

Synchrotron radiation X-ray powder diffraction data (SPDD) have been obtained for Ag[AgF4]2, Au[AuF4]2, Ag[AuF4], and Ag[AuF6]. Ag[AgF4]2 and Au[AuF4]2 are isostructural with Ag[AuF4]2, space group (SG) P2(1)/n, Z = 2, with the following: for Ag[AgF4]2 a = 5.04664(8), b = 11.0542(2), c = 5.44914(9) A, beta = 97.170(2) degrees; for Au[AuF4]2 a = 5.203(2), b = 11.186(3), c = 5.531(2) A, beta = 90.55(2) degrees. The structure of Ag[AgF4]2 was refined successfully (SPDD) applying the Rietveld method, yielding the following interatomic distances (A): AgII-F = 2.056(12), 2.200(13), 2.558(13); AgIII-F = two at 1.846(12), others = 1.887(12), 1.909(13), 2.786-(12), 2.796(12), 2.855(12). AgAuF4, like other AA'F4 salts (A = Na-Rb; A' = Ag, Au), crystallizes in the KBrF4 structure type, SG I4/mcm (140), Z = 4 with a = 5.79109(6), c = 10.81676(7) A. SPDD gave (in A) four AuIII-F = 1.89(1) and eight AgI-F = 2.577(7). SPDD for AgAuF6 confirmed that it has the LiSbF6 structure, SG R3, Z = 3, with a = 5.2840(2), c = 15.0451(6) A.