Substituenteneinflüsse auf Synthese und Eigenschaften von Hexakis[phosphanaurio(I)]methanium(2+)bis(tetrafluoroboraten) / Substituent Effects in Synthesis and Properties of Hexakis[phosphineaurio(I)]methanium(2 +) Bis(tetrafluoroborates)
2014
Schmidbaur, Hubert | Brachthäuser, Benno | Gamper, Siegfried | Schier, Annette | Steigelmann, Oliver
Polyaurated carbon complexes of the type [(L–Au)₆C]²⁺ with functionalized phosphine ligands have been prepared by the reaction of the phosphinegold(I) chlorides R(Ph)₂PAuCl (R = p-C₆H₄-Cl 2a,p-C₆H₄-Br 2b,p-C₆H₄-CH₃ 2c,p-C₆H₄-OCH₃ 2d,p-C₆H₄-COOH 2e, p-C₆H₄–N(CH₃)₂ 2f), R₂(Ph)PAuCl (R = p-C₆H₄-N(CH₃)₂ 2g) and R₃PAuCl (R = p-C₆H₄-N(CH₃)₂ 2h) with tetrakis(dimethoxyboryl)methane in HMPT at room temperature. Clearly depending on the different inductive and mesomeric effects, the preparation of the clusters with substituents like –CH₃ 3c, –OCH₃ 3d and –N(CH₃)₂ 3f needs shorter reaction times and the products show better solubility in organic solvents than those with functional groups like –Cl 3a, –Br 3b and –COOH 3e. The ³¹P magnetic resonance parameters are correlated with electronic effects of the substituents, but the chemical shift of the interstitial carbon atom in the ¹³C-NMR spectra is largely independent of the coordinating ligands. For the phosphinegold(I) chlorides 2f–h X-ray structure analyses have been performed.
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