Gas-Phase Metal Cyanide Chemistry: Formation, Reactions, and Proposed Linear Structures of Copper(I) and Silver(I) Cyanide Clusters

Controlled Degradation of a Ligand-Deficient Complex: From [{Cd(C6F5)(STrt)}4] to [{Cd(C6F5)(STrt)}3(OH)]− and [Cd(C6F5)(STrt)2]− (Trt = Triphenylmethyl)

“…The CϪS bonds of aliphatic thiols are in fact weaker than those of aromatic thiols. In some cases, CϪS scission reactions have even led to isolable sulfido complexes [10] . However, in the syntheses of the compounds 1Ϫ4 the use of triphenylmethanethiol-(ate) has been found unproblematic [11] .…”

Pentasupertetrahedral Clusters as Building Blocks for a Three‐Dimensional Sulfide Superlattice

“…Among chalcogenide clusters with various geometrical features, [2][3][4] tetrahedral clusters are of particular significance because they can act as pseudotetrahedral building blocks for the construction of zeolite-like open architectures. [5][6][7][8][9] Unfortunately, even though a number of superlattices built from supertetrahedral clusters have been reported, [10][11][12][13] relatively little progress has been made with other types of tetrahedral clusters.…”

“…[22,23] ICF-26 is built from a tetrahedral cluster denoted P2 (Figure 1). The P2 cluster (that is, Li 4 In 22 S 44 18À ) is the second member of a mathematical series of pentasupertetrahedral clusters Pn, thus termed because they can be conceptually constructed by coupling four supertetrahedral clusters onto the faces of an antisupertetrahedral cluster of the same order ( Figure 1). Supertetrahedral clusters are regular tetrahedronshaped fragments of the cubic ZnS type lattice and are denoted as Tn, where n is the number of metal layers.…”

“…Thus, the P1 cluster consists of four T1 clusters (MX 4 ) at the corners and one anti-T1 cluster (XM 4 A pentasupertetrahedral cluster is considerably larger than a supertetrahedral cluster of the same order, and hence it is difficult to prepare open-framework materials with pentasupertetrahedral clusters larger than P1. Even though supertetrahedral clusters as large as T5 are known, [12] the P2 cluster reported herein represents the largest known cluster of the Pn series.…”

“…As a result, all six metal sites of the anti-T2 clusters are disordered with each site occupied by 2/3 Li + cations and 1/3 In 3+ cations (Figure 1). This leads to an overall cluster formula of Li 4 In 22 S 44…”