title: Coordination of pyridinethiols in gold(I) complexes.
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.
authors.affiliation: Department of Chemistry, University of Helsinki, P.O. Box 55, FI-00014 University of Helsinki, Finland.
authors.forename: Minna T
authors.initials: MT
authors.lastname: Räisänen
authors.forename: Nino
authors.initials: N
authors.lastname: Runeberg
authors.forename: Martti
authors.initials: M
authors.lastname: Klinga
authors.forename: Martin
authors.initials: M
authors.lastname: Nieger
authors.forename: Michael
authors.initials: M
authors.lastname: Bolte
authors.forename: Pekka
authors.initials: P
authors.lastname: Pyykkö
authors.forename: Markku
authors.initials: M
authors.lastname: Leskelä
authors.forename: Timo
authors.initials: T
authors.lastname: Repo
mesh_terms: D018360:Crystallography, X-Ray; D006046:Gold / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D011725:Pyridines / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization; D013438:Sulfhydryl Compounds / Q000737:chemistry*
chemical_list: D011725:Pyridines; D013438:Sulfhydryl Compounds; D006046:Gold; C023666:pyridine