Coordination of pyridinethiols in gold(I) complexes

Inorg Chem. 2007 Nov 12;46(23):9954-60. doi: 10.1021/ic700453t. Epub 2007 Oct 11.

Abstract

High-yield synthesis of gold(I) thionato complexes, bis(pyridine-2-thionato)gold(I) chloride (1) and bis(pyridine-4-thionato)gold(I) chloride (2), are described. According to their solid-state structures, a linear coordination of Au(I), equiplanar coordination of the ligands and two weak gamma-agostic interactions are found in both of these complexes despite of different relative positions of N and S atoms in the pyridinethionato ligands. Density functional theory calculations on 1 and 2 reproduce the observed X-ray structures. Even though the C-H...Au interactions of Au(I) and two pyridine moieties (2.83 and 2.88 A in 1 and 2.86 A in 2) are relatively weak, according to calculations they seem to provide further stabilization for the coordination and orientation of the ligands. In 1 the shortest Au...Au distances of 3.50 A indicate that aurophilic interactions, even though weak, are present in the solid state, whereas in 2 these interactions are absent.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Crystallography, X-Ray
  • Gold / chemistry*
  • Magnetic Resonance Spectroscopy
  • Models, Molecular
  • Pyridines / chemistry*
  • Spectrometry, Mass, Electrospray Ionization
  • Sulfhydryl Compounds / chemistry*

Substances

  • Pyridines
  • Sulfhydryl Compounds
  • Gold
  • pyridine