New tetrathiahelicene-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−gold interaction of 3.1825(3) Å 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 ππ* 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.
Gold(I) Complexes of Tetrathiaheterohelicene Phosphanes / S. Cauteruccio, A. Loos, A. Bossi, M.C. Blanco Jaimes, D. Dova, F. Rominger, S. Prager, A. Dreuw, E. Licandro, A.S.K. Hashmi. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - 52:14(2013), pp. 7995-8004.
|Titolo:||Gold(I) Complexes of Tetrathiaheterohelicene Phosphanes|
|Parole Chiave:||gold(i)-catalyzed intramolecular hydroarylation; pyridine n-oxides; catalyzed cycloisomerizations; asymmetric catalysts; au(i) complexes; excited-states; molecules; crystal; ligands; model|
|Settore Scientifico Disciplinare:||Settore CHIM/06 - Chimica Organica|
|Data di pubblicazione:||2013|
|Digital Object Identifier (DOI):||http://dx.doi.org/10.1021/ic4005533|
|Appare nelle tipologie:||01 - Articolo su periodico|
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