Formation and X-ray structure of a novel tetradecanuclear silver cluster complex, Agl4(μ6-S)(SPh)12(PPh3)8 · 4CH3OH · 13H2O

Syntheses and Crystal Structures of the New Ag–S Clusters [Ag70S16(SPh)34(PhCO2)4(triphos)4] and [Ag188S94(PR3)30]

“…To our surprise, it evolved that the structure of 2 cannot be interpreted as part of the Ag 2 S structure. Related selenido and selenato complexes of silver (with less than 112 Ag atoms) are known to have structures composed of several shells, for example, [Ag 30 4 ], the largest Ag 2 Se cluster to be structurally characterized, adopt a distorted body-centered cubic arrangement in which the Ag atoms occupy the vacant positions and are surrounded by Se atoms in a distorted trigonal-planar or tetrahedral coordination environment. Disorder of Ag atoms, however, has also occurred in Ag 90 -, Ag 112 -, and Ag 172 clusters and seems to be a common feature in the structures of these clusters.…”

Synthesis and Crystal Structure of {[HNEt3]2n[Ag8Ag4/2(SC6H4tBu‐4)12]n·nC2H5OH} and Its Reaction Product with CS2

“…However, the S 2Ϫ ligands are essential for the formation of large clusters, since they bind the metal ions together. We have also found that in our previously reported large complexes, [Ag 14 (µ 6 -S)(SPh) 12 (PPh 3 ) 8 ]·4CH 3 OH·13H 2 O, [9] [Cu 14 (µ 2 -S)(SPh) 12 (PPh 3 ) 6 ], [10] and [S 4 Cd 17 (SPh) 24 (CH 3 OCS 2 ) 4/2 ] n · nCH 3 OH [11] etc., the S 2Ϫ ligands are formed from the reaction of CS 2 with RS Ϫ in solution. We suggest that when the metal thiolate compound is dissolved, the solvent causes it to dissociate into various ''active fragments'', including RS Ϫ , which reacts with CS 2 resulting in the formation of S 2Ϫ ions, as shown in Equation (1).…”

“…[6,7] We studied the insertion reaction of CS 2 into MϪS bonds (M ϭ Ag, Cu, Cd) and applied it to the synthesis of clusters. [8] It was found that the mononuclear insertion products (PPh 3 ) 2 M(S 2 CSR) (M ϭ Ag or Cu, R ϭ alkyl or aryl) react easily with various solvents to give a series large cluster complexes, such as [Ag 14 (µ 6 -S)(SPh) 12 (PPh 3 ) 8 ]·4CH 3 OH· 13H 2 O [9] and [Cu 14 (µ 2 -S)(SPh) 12 (PPh 3 ) 6 ] [10] etc. When cadmium thiolates were reacted with CS 2 in solvents in the absence of PPh 3 , several large CdϪS cluster complexes, for example [S 4 Cd 17 (SPh) 24 (CH 3 OCS 2 ) 4/2 ] n ·nCH 3 OH [11] and (Me 4 N) 2 [Cd 8 S(SPh) 12 Cl 4 ], [12] were obtained.…”

Isolation, structure and spectroscopic characterization of silver complexes of the zwitterionic thiolate Tab: [Ag(Tab)2](PF6), {[Ag3(Tab)4](PF6)3·2DMF}n, and [Ag14(μ6-S)(Tab)12(PPh3)8](PF6)12(Tab=4-(trimethylammonio)benzenethiolate)

“…4, the cluster framework of the dodecacation has an Ag 14 S 12 cage that is composed of Ag 8 cube, Ag 6 octahedron, and an S 12 icosahedron centred around a l 6 -sulfur atoms. The structure of the Ag 14 S 12 cage closely resembles that of neutral phenyl thiolate analogue [Ag 14 (l 6 -S)(SPh) 12 (PPh 3 ) 8 ] [28]. Each Ag atom in Ag 8 cube of 3 adopts a distorted tetrahedral geometry while that in Ag 6 octahedron has a trigonal geometry.…”