Synthesis and Molecular Structures of the Cationic Silver Complexes of the Polycondensed Aromatics Fluorene, Pseudorubrene, and Truxene

Abstract

We investigated the coordination behavior of AgI towards three polycondensed aromatic hydrocarbons (PAHs) in solution, in the solid state, and theoretically. Silver(I) trifluoromethanesulfonate (AgTfl) coordinates to fluorene to yield crystals of the composition {[(µ‐η2:η2‐fluorene)Ag2(Tfl)2]}n (1), the fluorene derivative 5,12‐diphenyl‐5,6;11,12‐di‐o‐phenylene‐5,12‐dihydrotetracene (pseudorubrene) reacts with silver(I) perchlorate to yield crystals of the composition bis[(η2‐pseudorubrene)(η2‐toluene)AgClO4]·toluenesolv (2), and the formation of the crystalline dimeric AgI sandwich compound [(µ‐η2:η2‐truxene)2(η1‐toluene)(µ‐H2O)Ag2(ClO4)2] (3) is accomplished by π‐coordination of the PAH truxene. In complexes 1–3, it is eminent from their crystal structures that the anionic silver moieties act as linking units between the PAH molecules. Theoretical calculations based on DFT methods of the aromatic bridging ring ligands substantiate the experimentally observed selective AgI coordination for each of the three PAH molecules fluorene, pseudorubrene, and truxene.

Anionic Bismuth Oxido Clusters with Pendant Silver Cations: Synthesis and Structures of {[Bi4(µ3‐O)2(TFA)9Ag(tol)2]2} and {Bi4(µ3‐O)2(TFA)10(AgPPh3)2}n

“…For the C11X and C13X ring interactions, the centroid-centroid distance is 4.386 Å; for the C12X ring interactions, the centroid-centroid distance is 4.063 Å, consistent with literature values. [51][52][53] Thus, the crystallographic transition for the different observed unit cells can be ascribed to the more efficient packing of the {[Bi 4 (μ 3 -O) 2 (TFA) 9 Ag(tol) 2 ] 2 } units due to the creation of a π-π stacking network between the bound toluene rings.…”

Facile Route to Silver Triarene Borate Salts, [Ag(arene)3][B(C6F5)4]: Thermodynamics, Structure, and Bonding

“…Additionally, they studied the formation of AgClO 4 benzene, toluene, m -xylene, and mesitylene complexes by absorption measurements. In the 1970s cationic olefin complexes of copper were above all the focus of research. − In 1990 Duncan et al and in 1994 Afzaal and Freiser studied the gas-phase photodissociation of [Ag­(arene) n ] + (arene = benzene, toluene) and only sporadically were silver complexes with aromatic ligands targeted again. − While Ag + arene π complexes have been observed before, ,− the first [Ag­(arene) 3 ] + -containing salt, Ag­(CHPh 3 )­(1-Me-CB 11 F 11 ), was structurally characterized by Strauss et al The structure and synthesis of [Ag­(benzene) 3 ]­[B­(C 6 F 5 ) 4 ], which was isolated from the reaction of Li­[B­(C 6 F 5 ) 4 ] and aqueous AgNO 3 after recrystallization from hot benzene (Scheme ; arene = benzene), were reported by Kitagawa et al (Figure ). To date, there have been a variety of silver complexes with alkenes, − arenes, ,,− and even fluorine-substituted arenes. − …”