Silver cages

Figure 11.11. Ligands 5 and 6 used in the construction of silver cage-like complexes.

G.-C. Guo, G-D. Zhou and T. C. W. Mak, Structural variation in novel double salts of silver acetylide with silver nitrate fully encapsulated acetylide dianion in different polyhedral silver cages. J. Am. Chem. Soc. 121, 3136—4-1 (1999). 

By analogy to aurophilicity, argentophilicity has been demonstrated to exist in silver cluster complexes. In the crystal structures of a variety of silver double and multiple salts containing a fully encapsulated acetylide dianion C (IUPAC name acetylenediide) in different polyhedral silver cages (see Fig. 14.3.11), there exist many Ag- -Ag contacts shorter than twice the van der Waals radius of silver (2 x 170 = 340 pm). Further details are given in Chapter 20. 

Mixed-valent silver(I,II) compounds containing Ag2<22 To investigate the effect of coexisting metal ions on the assembly of polyhedral silver cages, macrocyclic (V-donor ligand 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane (tmc) has been used for in situ generation... 

Figure 23. Rhombohedral core of the silver cage [Agi4(C=Ct-Bu)i2Cl][OH] (X = OH).

Figure 5 (a) Structure of silver cage complexes [Agi4(C=C Bu)i2X]OH = Cl, Br) showing the rhombic dodecahedron of silver atoms (solid bonds) and the encapsulation of a halide anion at the center of an octahedron of type 2 silver atoms. Silver atoms of types 1 and 3 cap the faces of this octahedron and define a cubic array.(b) Mixed-metal Aui2Agi2Pt core in [(PhsP) ioAui2Agi2PtCl7]Cl the Pt atom and one Au atom randomly occupy the pair of AP sites ... 

ZhaoX-L, Mak TCW (2004) Silver cages with encapsulated acetylenediide as building blocks for hydrothermtil synthesis of supramolecular complexes with n-cyanopyridine and pyridine-n-carboxamide (n = 3,4). Dalton Trans 3212-3217... 

Reaction of [Ag(N03)(/i-dppa)] (80) with KCl and excess dppa was reported to give the di-silver cage [(AgCl)2(/i-dppa)3] 131e (Fig. 2.53) in seeming contrast to the reactions with KBr and KI that result in polymer 82 (Sect. 2.3.2 Fig. 2.27), but the evidence is solely based on elemental analyses, which are identical for the cage and polymeric structure and their resemblance with copper cages 124 [86]. 

---