Structure of Ag(CHPh₃)(1-Me-CB₁₁F₁₁). Trigonal-Planar Ag(Arene)₃⁺ Cations, Polymeric {Ag(CHPh₃)⁺}_∞ Triangular-Net Layers, and Partially Aligned Interstitial Carborane Anions in a Polar Crystal

Abstract

The synthesis and structure of the layered solid Ag(CHPh3)(1-Me-CB11F11) are described. The compound crystallized from dichloromethane solution in the polar space group Pna21 (orthorhombic, C21H19AgB11F11, a = 21.6736(7) Å, b = 8.7163(3) Å, c = 14.5737(5) Å, Z = 4). The structure consists of layers of {Ag(CHPh3)+}∞ polycations with 1-Me-CB11F11 - anions filling half of the trigonal prismatic holes defined by six Ag+ ions from successive {Ag(CHPh3)+}∞ layers. The {Ag(CHPh3)+}∞ triangular-net layers contain the first example of a rigorously trigonal-planar Ag(arene)3 + complex. There are no contacts between the Ag+ cations and the 1-Me-CB11F11 - superweak anions shorter than 3.29 Å. The idealized C 5 axes of the per-B-fluorocarborne anions are partially aligned along the crystallographic c axis.

Synthesis, structure, and reactivity of AlMe2(1-Me-CB11F11): An AlMe2+ cation-like species bonded to a superweak anion

“…The rhomb has three Á Á Á distances, 6.826, 7.495, and 9.055 Å . The short 6.826 Å distance is among the shortest observed for a 1-R-CB 11 F 11 À or B 12 F 12 2À compound [11][12][13][14], and this distance in [AlMe 2 (1-Me-CB 11 F 11 )] 2 is between anions that are almost perfectly dovetailed (the relevant dihedral angle is 84.58 instead of 908; the four FÁ Á ÁF distances are 2.697, 2.946, 2.978, and 3.083 Å ). Interestingly, the 9.055 Å distance is between two anions that point directly at one another (see the highlighted F and C atoms near the bottom part of Fig.…”

“…Toluene and toluene-d 8 were distilled from sodium. The compound Ag(C 6 H 6 )(1-Me-CB 11 F 11 ) was prepared by a literature procedure [11]. The compound [CPh 3 ][1-Me-CB 11 F 11 ] was prepared by reacting Ag(C 6 H 6 )(1-Me-CB 11 F 11 ) with CPh 3 Cl.…”

Convenient Access to Gallium(I) Cations through Hydrogen Elimination from Cationic Gallium(III) Hydrides

“…On the other hand, compound 1 is rather robust, whereas compound 3 can experience anion decomposition under harsh conditions (vide infra); [Ga­(benzene) 2 ]­[GaCl 4 ] is known to suffer from various decomposition modes dependent on conditions . In compound 3 , each gallium center is coordinated to phenyl groups from two different triphenylmethane molecules, leading to a coordination polymer (Figure S47) similar to the silver compound [Ag­(Ph 3 CH)]­[MeCB 11 F 11 ] . In addition, there are two additional phenyl groups in contact with the gallium center in an η 2 fashion with rather long average distances of 3.461 and 4.128 Å, resulting in an overall bowl-shaped environment for the gallium center (Figure S48).…”

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. − …”