Gold(I) complexes bearing pnn-ligands: an unprecedented twelve-membered ring structure stabilized by aurophilic interactions
- Autor(en)
- Michel Fleck, Uwe Monkowius, Hartmut Yersin, Manfred Zabel
- Abstrakt
The PnN-ligands Ph2Pqn, 1, Ph2Piqn, 2, Ph2Ppym, 3, and the AsnN-ligands Ph2Asqn, 4,Ph2Asiqn, 5, (Ph = phenyl, qn = 8-quinoline, iqn = 1-isoquinoline, pym = 2-pyrimidine) have beensynthesized, the ligands 2 and 5 for the first time. Their ligand properties were probed by the synthesisof gold(I) complexes. Reaction with (tht)AuCl (tht = tetrahydrothiophene) yielded the chlorogoldcomplexes Ph2RP-Au-Cl (R = qn, 6; iqn, 7; pym, 8) and Ph2RAs-Au-Cl (R = qn, 9; iqn,10) in high yields. Further treatment of 7 and 8 with one equivalent of AgBF4 provided the complexes[(Ph2Piqn)Au]BF4, 11, [(Ph2Ppym)Au]BF4, 12, and [(Ph2Piqn)Au(tht)]BF4, 14. For comparison,the previously reported complex [(Ph2Ppy)Au]BF4 (py = pyridine), 13, was re-investigated. Thecompounds were characterized by elemental analyses, mass spectrometry and NMR spectroscopy. Inaddition, the solid-state structures of 2, 3, 6, 7, 9 - 14 have been determined by X-ray crystallography.The chloro-gold compounds crystallize in the common rod-like structure known from R3EAuCl(R = aryl, E = P, As) complexes without further aggregation via aurophilic interactions. In all casesthe phosphine acts as a monodentate ligand. In the solid state compounds 11 - 13 feature an unprecedentedcyclic trinuclear aggregation pattern, in which the Au(I) atoms are linearly coordinatedby the bridging phosphine ligands forming a cyclic (P-Au-N)3 arrangement. The resulting twelvememberedring is further stabilized by Au ... Au interactions. Due to the presence of these Au ... Aucontacts, 11 - 13 are emissive in the solid state but not in solution.
- Organisation(en)
- Institut für Mineralogie und Kristallographie
- Externe Organisation(en)
- Johannes Kepler Universität Linz, Universität Regensburg
- Journal
- Zeitschrift für Naturforschung. Section B: A Journal of Chemical Sciences
- Band
- 64
- Seiten
- 1513-1524
- Anzahl der Seiten
- 12
- ISSN
- 0932-0776
- Publikationsdatum
- 2009
- Peer-reviewed
- Ja
- ÖFOS 2012
- 105113 Kristallographie
- Link zum Portal
- https://ucrisportal.univie.ac.at/de/publications/f5fcb8c8-21fc-4483-babe-1b2523fd912d