Gold(I) Complexes of Tetrathiaheterohelicene Phosphanes

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• 作者：Silvia Cauteruccio ; Annette Loos ; Alberto Bossi ; Maria Camila Blanco Jaimes ; Davide Dova ; Frank Rominger ; Stefan Prager ; Andreas Dreuw ; Emanuela Licandro ; A. Stephen K. Hashmi
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：July 15, 2013
• 年：2013
• 卷：52
• 期：14
• 页码：7995-8004
• 全文大小：486K
• 年卷期：v.52,no.14(July 15, 2013)
• ISSN：1520-510X

文摘

New tetrathia[7]helicene-based (7-TH-based) gold(I) complexes 6 and 7 have been readily prepared by reaction of the respective phosphine ligands 2 and 3 with Au(tht)Cl in a 1:1 and 1:2 molar ratio, respectively. These complexes have been fully characterized by analytical and spectroscopic techniques as well as quantum chemical calculations. The molecular structure of dinuclear complex 7 has been determined by single-crystal X-ray diffraction, showing a gold鈥揼old interaction of 3.1825(3) 脜 and a significant contraction of the 7-TH total dihedral angle. Au(I) complex 7 displays luminescence emission at room and low temperature in diluted solution and in the solid state. Quantum chemical calculations show that the luminescence emission at room temperature is primarily due to slightly perturbed fluorescence emission from purely 蟺蟺* excited states of the conjugated helicene scaffold. At 77 K phosphorescence emission is displayed as well. Preliminary studies on the use of 6 and 7 as catalysts in typical Au(I)-catalyzed cycloisomerizations have demonstrated the reactivity of these systems in the intramolecular allene hydroarylations and the hydroxycarboxylation of allene-carboxylates.