Darstellung,Schwingungsspektrum und Kristallstruktur von (n‐Bu4N)2[(W6Cl)F] · 2 CH2Cl2 und 19F‐NMR‐spektroskopischer Nachweis der gemischten Clusteranionen [(W6Cl)FCl]2–, n = 1–6 |
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Authors: | M Stallmann W Preetz |
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Abstract: | Synthesis, Vibrational Spectra, and Crystal Structure of ( n ‐Bu4N)2(W6Cl )F ] · 2 CH2Cl2 and 19F NMR Spectroscopic Evidence of the Mixed Cluster Anions (W6Cl )F Cl ]2–, n = 1–6 The reaction of (n‐Bu4N)2(W6Cl)Cl] with CF3COOH in dichloromethane gives intermediately a mixture of the cluster anions (W6Cl)(CF3COO)Cl]2–, n = 1–6. By treatment with NH4F the outer sphere coordinated trifluoracetato ligands are easily substituted and the components of the series (W6Cl)FCl], n = 1–6 are formed and characterized by their distinct 19F NMR chemical shifts. An X‐ray structure determination has been performed on a single crystal of (n‐Bu4N)2(W6Cl)F] · 2 CH2Cl2 (orthorhombic, space group Pbca, a = 15.628(4), b = 17.656(3), c = 20.687(4) Å, Z = 4). The low temperatur IR (60 K) and Raman (20 K) spectra are assigned by normal coordinate analysis based on the molecular parameters of the X‐ray determination. The valence force constants are fd(WW) = 1.89, fd(WF) = 2.43 and fd(WCl) = 0.93 mdyn/Å. |
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Keywords: | Tungsten Clusters Tungstates Crystal structure NMR spectroscopy (19F) Vibrational spectroscopy |
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