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.

Metallophilic interactions in polymeric group 11 thiols

“…Polymer [33] b E int = 0.429G(r) [34] The QTAIM analysis of (1) confirmed the presence of nine bond critical points (BCPs) (3, -1) for Cu⋅⋅⋅Cu contacts in the copper polymer and the presence of four BCPs for Au⋅⋅⋅Au contacts in the gold chain (3) 3.193950 S 7.769098 -1.266235 3.193950 N 6.499587 -5.623467 3.193950 C 7.267034 -2.935613 3.193950 C 8.214485 -3.967186 3.193950 H 9.142476 -3.761203 3.193950 C 7.797315 -5.284573 3.193950 H 8.451652 -5.972702 3.193950 C 5.577677 -4.645113 3.193950 H 4.658199 -4.880740 3.193950 C 5.923089 -3.314767 3.193950…”

“…The structure of 3 has been reported earlier [33]. However, the current structure is based on higher quality data and therefore includes also the hydrogen atoms that were previously not detected.…”

Tuning electronic structures of uranyl fluorides via increasing equatorial pyridyl number and extending pyridyl conjugation

“…[1][2][3][4] Many of their transition metal complexes have been found to show peculiar optical, electrochemical and magnetic properties. [4] Polypyridyl ruthenium(II) complexes, for instance, have achieved great success as photosensitizers in dye-sensitized solar cells (DSSCs), because exhibiting intense and broad metal-to-ligand charge transfer (MLCT) absorption bands in the visible-light area.…”

“…To well understand the physicochemical behavior of uranyl complexes, we have theoretically examined electronic structures of a series of N-coordinating uranyl 3 fluorides. We started to optimize a single-pyridyl uranyl fluoride [(UO 2 )(py)F 4 ] 2-(1a).…”

“…While increasing the pyridyl number, we calculated [(UO 2 )(py) 3 with one less fluorine ligand in the equatorial plane. So far, complexes structurally analogous to 1a′, 1a″, 3a and 4a have been experimentally synthesized and characterized by X-ray crystal diffraction [33][34][35][36][37].…”