Syntheses and Structures of Niobium Copper Chalcogenido Clusters: [Cu4Nb6Se12O(PMe3)10][Cu4NbSe4Cl2(PMe3)4]⋅ 1.5 DMF, [Cu4Nb2Se6(PMe3)8], (NEt4)[Cu6Nb2S6Cl5(PEt3)6], and [Cu6NbTe3(Te2)2(PEt3)6][CuCl2] This work was supported by the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie.

Abstract

Silylated chalcogenides (Me3Si)2E (E=S, Se, Te) grant access to novel Nb–Cu chalcogenido clusters with as yet unknown molecular structures. Dimetallic Nb–Cu selenido clusters [Cu4Nb6Se12O(PMe3)10][Cu4NbSe4Cl2(PMe3)4] (the structure of the cation is depicted; Cu: black, Nb: dark gray, P: light gray, Se: white O: small white) and [Cu4Nb2Se6(PMe3)8] were isolated from reactions of (Me3Si)2Se with Nb‐Cu‐Se units that were formed in situ. Reactions of CuCl and NbCl5 towards (Me3Si)2S or (Me3Si)2Te produce the compounds (NEt4)[Cu6Nb2S6Cl5(PEt3)6] and [Cu6NbTe3(Te2)2(PEt3)6][CuCl2], respectively.

Facile Access to the Hydrazone Functionalized PdGeS Cluster [{RNGe(μ-S)3}4Pd6] from the Thiogermanate Anion [{RNGe}2(μ-S)2S2]2−

“…The R N -ligated PdGeS cluster core in 2 is topologically identical to the quoted, Dmp-shielded NiGeS cluster. Very similar topologies were observed in two further ternary clusters, the PR 3 ligated cation in [Cu 4 Nb 6 Se 12 O(PMe 3 ) 10 ][Cu 4 NbSe 4 Cl 2 (PMe 3 ) 4 ]·1.5DMF and the purely inorganic M/Ge/Se anion in [Ba 3 (H 2 O) 15 ][Mn 6 (H 2 O) 6 (μ 6 -Se)(GeSe 4 ) 4 ]·9H 2 O . In these compounds, the Nb or Mn atoms possess octahedral coordination, achieved by a central, μ 6 -bridging Se ligand and additional ligands pointing away from the M 6 apexes, whereas in 2 , the d 8 configuration of the Pd II centers leads to a preference of a square-planar coordination.…”

Ternary Mixed‐Valence Organotin Copper Selenide Clusters

“…The family of discrete metal chalcogenide clusters with a ternary inorganic core comprises a diversity of structural motifs and compositions, ranging from ligand‐stabilized neutral heterocubanes to huge anionic supertetrahedra, and from clusters of moderate size to compounds on a nanometer scale . These feature combinations of different transition metal atoms or different main group metal atoms, or both, or they combine atoms of transition metals and lanthanides …”

Novel Luminescent Tetranuclear and Pentanuclear Copper(I)−Dithiolates

“…As an emerging class of inorganic materials, polynuclear Cu I −chalcogenide species are drawing considerable attention because of their rich photophysics, photochemistry, and structural diversity. − Many novel structures have been discovered in the search for emissive Cu I clusters as exemplified by the compound [Cu 4 (μ 2 -dppm) 4 (μ 4 -S)](PF 6 ) 2 2a,b,e which displays an unprecedented square pyramid comprising a square Cu I 4 core capped by a tetracoordinate S 2- ion. The work underscored the function of the S atom as a nucleating center for copper ions, and in fact, monothiolates, 1,1-dithiolates, and 1,2-dithiolates 5 have long been used in the synthesis of Cu I aggregates of high nuclearity, many of them displaying intriguing structures such as icosahedral [Cu 8 (S 2 R) 6 ] 4- (R = CC(CN) 2 ) 4a and {Cu 9 (μ 2 -dppm) 4 [S 2 CC(CN)P(O)(OEt) 2 ] 4 }(PF 6 ) 4c.…”