Gold complexes with heterocyclic thiones as ligands. X-Ray structure determination of [Au(C₅H₅NS)₂]ClO₄

Gold–Gold Interactions

“…Among them complex [Au(SNC 5 H 5 ) 2 ]ClO 4 has been studied by X-ray diffraction. Five of the six cations in the cell are linked by short Au-Au contacts and the sixth cation is monomeric [62]. Association of molecules in the previous examples is in most cases linear.…”

Hydrogen‐Bonded Network and Layered Supramolecular Structures Assembled from ClO4− Counterions with Unprecedented Monomeric [AgL2]+ and Chain Polymeric [AgL2]nn+ Complex Cations (L = Thioamide or Thiourea‐Like Ligands)

“…Whereas (Ϫα, α) is a general notation for twist angles that would hold for the two ideal orientations attributable to electron-deficient bridge bonding, the relation ∆ tw ϭ 180 Ϫ 2α applies only to the present situation. As reported for M(tu) 2 Cl (M ϭ Cu, Ag), [55,56] to the best of our knowledge the only known complexes for which sulfur-bridge bonding has been explained according to model D, the overall effect of both stereochemical constraints and electronic factors leads to a deviation of the thiourea plane, and thus of the N···N line, by about 8°from the direction of the M···MЈ line, the tilt angle being reasonably close to 90°. For electron-deficient sulfur-bridged bonding with only two electrons supplied by the thioamide (CϭS) pπ-MO (type D), probable general orientations would be given, though on the basis of only those two complexes, by pairs of twist angles (Ϫα 1 , α 2 ), with ∆ tw ϭ 180 Ϫ (α 2 ϩ |α 1 |) and suitable α i values both falling within the approximate range 40 Յ |α i | Ͻ 65°.…”

“…[61] These bridging ligand molecular orbitals (HOMOs), each accommodating one electron pair, are able to interact with two vacant tetrahedral sp 3 or other hybrid orbitals, one for each silver atom of the AgϪSϪAg bridge. Considerations of this kind, aimed at proposing an MϪS bonding model from an analysis of the stereochemistry, have previously been performed for dinuclear [1,32] and some polymeric [22,23,27,55,56] sulfur-bridged complexes of thioamide or thiourea ligands. All these earlier examples, however, contain both bridging and terminal ligands, which is not the case here.…”

“…Ϫ [51] or Cl Ϫ ; [52] L ϭ tu, X ϭ Br Ϫ [53] or ClO 4 Ϫ ; [54] L ϭ py2tH, X ϭ ClO 4 Ϫ ; [55] L ϭ dmtu or detu, X ϭ ClO 4 Ϫ . [56] The [Au(etu) 2 ] ϩ cation in [Au(etu) 2 ]Cl·H 2 O is somewhat more distorted, with an SϪAuϪS angle of 167.1°, owing to the cis configuration of the heterocyclic rings of the two ligands.…”

Gold(I)-diphenylphosphinomethane–arylazoimidazole: synthesis and multinuclear NMR investigation

“…The ''luminescent switch'' for the detection of VOCs using gold(I) dimers, following the pioneering work by Mann and co-workers [2] on absorption and emission spectra of vapochromic platinum(II) and palladium (II) compounds, shows that phenomena of this kind of luminescent gold(I) compound holds great potential for analytical applications. Hence running years have witnessed a great deal of interest in the synthesis of the complexes of gold with a-diimine type of ligands because of their photochemical, catalytic properties [2,6,11], energy conversion and ability to serve as building blocks in supramolecular arrays [12][13][14][15][16][17][18]. Researchers have been engaged in modifying the properties of Au-pyridine complexes by replacing the ligands of other donor centres, altering the steric and electronic properties of the ligands, differently substituted polypyridine mixed donor heterocycles.…”