Coordination of pyridinethiols in gold(I) complexes.
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.
Räisänen
Minna T
MT
Department of Chemistry, University of Helsinki, P.O. Box 55, FI-00014 University of Helsinki, Finland.
Runeberg
Nino
N
Klinga
Martti
M
Nieger
Martin
M
Bolte
Michael
M
Pyykkö
Pekka
P
Leskelä
Markku
M
Repo
Timo
T
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*
D011725:Pyridines; D013438:Sulfhydryl Compounds; D006046:Gold; C023666:pyridine