First Examples of Au^I−X−Ag^I Halonium Cations (X = Cl and Br)

Abstract

Novel {[(mu-PAnP)(AuX)2]2Ag}+SbF6- halonium ions (X = Cl, Br; PAnP = 9,10-bis(diphenylphosphino)anthracene) were synthesized from the reactions between (mu-PAnP)(AuX)2 and 1/2 mol equiv of AgSbF6. The compounds feature an unprecedented distorted Au4X4 dodecahedron which encapsulates a silver(I) ion at its center. The halonium ions are stabilized by collective actions of metallophilic Au-Ag, aromatic pi-pi, and Ag-X interactions.

Walkable Dual Emissions

“…On the other hand, if other metallic blocks complexed with the same ligand, dual emissions may also be provided2021. However, as the energy levels of metallic blocks and the aromatic ligands are susceptible to the external environment, the two emissions are active during altering experimental conditions22.…”

Di-μ-bromido-tris(triphenylphosphine)-1κP,2κ2P-disilver(I) tetrahydrofuran 0.85-solvate

“…For general background on triphenylphosphinesilver(I) complexes, see: Whitcomb & Rajeswaram (2006); Whitcomb & Roger (1996); Mann et al (1937); Teo & Calabrese (1976); Bowmaker et al (1993); Olmstead et al (2004); Zhang et al (2003); Lobana et al (2008); Cingolani et al (2003). For the sensitization of photothermographic materials by coordination polymers formed by the reaction of triphenylphosphine with silver(I) salts, see : Freedman (1994).…”

“…Since the first tertiary phosphine silver (I) complexes of the type [AgXL n ] (L is tertiary phosphine; n is 1-4; X is a coordinating or noncoordinating anion) were prepared in 1937 by Mann et al (1937), many complexes have been obtained by the reaction of triphenylphosphine with an appropriate silver (I) salt (Whitcomb & Rajeswaram, 2006;Whitcomb & Roger, 1996;Teo et al, 1976;Bowmaker et al, 1993;Olmstead et al, 2004;Zhang et al, 2003;Lobana et al, 2008;Cingolani et al, 2003).…”

Gold–Heterometal Interactions and Bonds

“…Within the heterometallic cation the Ag atom interacts strongly with six Au (I) atoms from two cyclic Au 3 C 3 N 3 moieties [Au-Ag 2.731(2)-2.922(2) Å] and an infinite columnar polymer of the type Á Á ÁBBABBAÁ Á Á is formed through weak intercation aurophilic interactions [Au-Au 3.268(1) Å]. The reaction of (m-PAnP) (AuX) 2 with AgSbF 6 , instead of precipitating AgX, afforded the isolation of isostructural complexes [{(m-PAnP)(AuX) 2 } 2 Ag(SbF 6 )] n [X ¼ Cl 441, Br 442], which display unprecedented Au(I)-X-Ag(I) halonium cations [600]. The compounds also consist of helical coordination polymers, with silver(I) ions encapsulated at the center of a distorted Au 4 X 4 dodecahedron described by the Au and X atoms of four neighboring (m-PAnP)(AuX) 2 units.…”

“…The compounds also consist of helical coordination polymers, with silver(I) ions encapsulated at the center of a distorted Au 4 X 4 dodecahedron described by the Au and X atoms of four neighboring (m-PAnP)(AuX) 2 units. In addition to the weakly coordinated halide atom, the Au-Ag separations [3.2180(4) Å in 441, and 3.2701(5) Å in 442] suggest weak d 10 -d 10 metallophilic interactions, which contribute together with Ag-halide and p-p interactions to the stabilization of the halonium cations [600].…”