Gold(I) Complexes Bearing P boolean AND N-Ligands: An Unprecedented Twelve-membered Ring Structure Stabilized by Aurophilic Interactions

作者：Monkowius Uwe^*; Zabel Manfred; Fleck Michel; Yersin Hartmut

来源：Zeitschrift fur Naturforschung Section B-A Journal of Chemical Sciences, 2009, 64(11-12): 1513-1524.

• Gold(I) Complexes
• Phosphines
• Arsines
• P boolean AND N Ligands
• Luminescence
• Aurophilic Interactions

The P boolean AND N-ligands Ph(2)Pqn, 1, Ph(2)Piqn, 2, Ph(2)Ppym, 3, and the As boolean AND N-ligands Ph(2)Asqn, 4, Ph(2)Asiqn, 5, (Ph = phenyl, qn = 8-quinoline, iqn = 1-isoquinoline, pym = 2-pyrimidine) have been synthesized, the ligands 2 and 5 for the first time. Their ligand properties were probed by the synthesis of gold(I) complexes. Reaction with (tht)AuCl (tht = tetrahydrothiophene) yielded the chloro-gold complexes Ph(2)RP-Au-Cl (R = qn, 6; iqn, 7; pym, 8) and Ph(2)RAs-Au-Cl (R = qn, 9; iqn, 10) in high yields. Further treatment of 7 and 8 with one equivalent of AgBF(4) provided the complexes [(Ph(2)Piqn)Au]BF(4), 11, [(Ph(2)Ppym)Au]BF(4), 12, and [(Ph(2)Piqn)Au(tht)]BF(4), 14. For comparison, the previously reported complex [(Ph(2)Ppy)Au]BF(4) (py = pyridine), 13, was re-investigated. The compounds were characterized by elemental analyses, mass spectrometry and NMR spectroscopy. In addition, 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 R(3)EAuCl (R = aryl, E = P, As) complexes without further aggregation via aurophilic interactions. In all cases the phosphine acts as a monodentate ligand. In the solid state compounds 11-13 feature an unprecedented cyclic trinuclear aggregation pattern, in which the Au(I) atoms are linearly coordinated by the bridging phosphine ligands forming a cyclic (P-Au-N)(3) arrangement. The resulting twelve-membered ring is further stabilized by Au center dot center dot center dot Au interactions. Due to the presence of these Au center dot center dot center dot Au contacts, 11-13 are emissive in the solid state but not in solution.

• 出版日期2009-12