Syntheses and Crystal Structures of the AgS Cluster Compounds [Ag₇₀S₂₀(SPh)₂₈(dppm)₁₀] (CF₃CO₂)₂ and [Ag₂₆₂S₁₀₀(StBu)₆₂(dppb)₆]

Abstract

Dedicated to Professor Hans Bock on the occasion of his 75th birthday Numerous reports have described the syntheses and structures of metal-rich compounds. In recent years, research activities in this field have been very successful, especially in the synthesis of heteropolyacids and clusters of maingroup and transition-metal elements. 20 ]. [1][2][3] Another area of interest is the preparation of metal chalcogenide clusters.[4] Recently, the synthesis and crystal structure of an ionic compound containing the anion [Cd 16 In 64 S 134 ] 44À was reported.[5] The size of this structure is within the order of magnitude of nanocrystalline materials.Metal-rich complexes are also known from chalcogenides of other electron-rich transition-metal elements. [6] and other Cu and Ag chalcogenide clusters that were synthesized by using tertiary phosphanes to inhibit the competing formation of the thermodynamically preferred binary metal-chalcogenide phases. Quantum chemical investigations showed that clusters of this type are metastable compounds whose collapse is kinetically prevented. [7] There is some evidence that selenide and telluride clusters, such as [Cu 146 [15] These compounds form in high yields upon

Functional ligands and complexes for new structures, homogeneous catalysts and nanomaterials

“…The potential of cluster complexes to mediate unique bond forming/breaking reactions [83] or of heterobimetallic complexes to display reactivity patterns that are unknown for their homometallic analogs, as recently observed in the dimerization of methylacrylate promoted by a Ni-Mo complex [84] is also noteworthy. The diversity provided by synthetic chemistry remains a fascinating challenge and new bonding situations continue to be discovered [85], in particular in cluster chemistry which offers unique opportunities for aesthetically pleasing mixed-metal, often dynamic molecules (Mn 4 Pd 4 helices, Fe 2 HgCu molecular torsion pendulum) [86], very large clusters [56,87], giant single-molecule magnets [88] and extended structures [89], including systems that move towards bimetallic wires [90].…”

High-nuclearity cobalt coordination clusters: Synthetic, topological and magnetic aspects

“…Edited Feb 6 10 mineral [75,76] or have found analogies with motifs found in main group chemistry [16,28]. Our inspiration was from the concept of using a topological representation for 2D and 3D coordination polymers and Metal-Organic Frameworks -MOFs [77,78].…”

Metal Chalcogenide Clusters on the Border between Molecules and Materials

“…[16] Using silver benzoate as a metal source and a mixture of S(SiMe 3 ) 2 and tBuSSiMe 3 in the presence of the bidentate ligand 1,4-bis(diphenylphosphino)butane (dppb) yields the ellipsoid shaped [Ag 262 S 100 (StBu) 62 (dppp) 6 ]. [17] A similar reaction using 1,4-bis(diphenylphosphanylmethyl)benzene (dppxy) as a ligand leads to the formation of [Ag 344 S 124 (StBu) 96 ] where no phosphine ligands are present in the ligand shell; [18] nevertheless the presence of the phosphine is essential for the cluster formation. Recently we established a two-step route for the synthesis of giant silver sulphide clusters.…”

“…4). Arrangements of neutral Cd 8 , Cd 17 and Cd 32 -sulfide nanocluster frameworks have also been prepared, where the frameworks are linked in the crystal lattice via bifunctional ligands (e.g., 4,4 0 -bipyridine) at the apical sites. [30] The lowest-lying transition observed in the UV-visible absorption spectra for the Cd 17 -, Cd 32 -, and Cd 54 -sulfide nanoclusters have been determined (4.26, 3.79, and 3.51 eV, respectively).…”