A new metal cluster system containing a cube of metal atoms

Copper Complexes with (2,7‐Di‐tert‐butylfluoren‐9‐ylidene)methanedithiolate: Oxidatively Promoted Dithioate Condensation

“…However, their composition and the copper/dithiolate/phosphane ratio were unambiguously determined by means of elemental analyses and 1 H NMR spectroscopy (see Experimental Section for details). The 1 H, 13 C, and 31 P NMR spectroscopic data are consistent with highly symmetrical structures containing equivalent dithiolato ligands and phosphanes. Given the preference of Cu I for a trigonal planar or tetrahedral coordination geometry and its tendency to form high nuclearity thiolato complexes with extensive cuprophilic interactions, a dinuclear formulation for 5a-d is unlikely.…”

“…[12][13][14][15][16][17][18][19][20] Previously described 1,1-ethylenedithiolates that have been used for the preparation of copper complexes are limited to those with X = Y = CN (i-mnt), CO 2 R [R = Me (dmd), Et (ded), tBu (tBu-ded)] and X = CN and Y = P(O)(OEt) 2 (cpdt). The anionic Cu I clusters [Cu 8 -(i-mnt) 6 ] 4-, [12,13,19] [Cu 8 (ded) 6 ] 4-, [14] and [Cu 8 (tBuded) 6 ] 4- [15,16] stand out as the best-studied 1,1-ethylenedithiolato complexes of copper, and theoretical calculations have been carried out in order to understand the bonding in the Cu 8 S 12 core. [21,22] The tetranuclear cluster [Cu 4 (i-mnt) 4 ] 4-has been obtained from the reaction of the sulfur-rich dithiolato cluster [Cu 6 {S 3 C=C(CN) 2 } 6 ] 6-with triphenylphosphane.…”

Copper‐Rich Framework Selenoarsenates Based on Icosahedral Cu8Se13 Clusters

“…In contrast, these were attainable though covalent bonding between chalcogen and carbon or phosphorus atoms in the discrete molecular clusters. [39][40][41][42]48,49] Furthermore, the valent state of main group cations can also influence the kind of icosahedral clusters. For example, Ge 4+ and Sn 4+ can induce icosahedral Cu 8 S 12 cluster built up from corner sharing of eight CuS 3 triangle, [26][27][28]33] while As 5+ or Sb 5+ can induce Cu 8 Se 13 and Cu 8 S 13 cluster, [25] respectively, in which an additional Se 2-or S 2-were incorporated at the core site of the cluster, and lead to distorted tetrahedral coordination of each copper ions.…”

Electron count versus structural arrangement in clusters based on a cubic transition metal core with bridging main group elements

“…The long Cu-(/18-S) contacts measured in this species, 2.694 X, suggest that the copper-sulfur bonding is somewhat ionic in character, as confirmed by Fenske-Hall MO calculations which indicate a highly negatively charged interstitial S atom [51]. The long Cu-Cu separations, 3.105 .&, are considerably longer than the Cu-Cu distances measured in the non-centered 128-MVE copper Cu8S~2 species (see above) [32][33][34]. Despite these long distances which might indicate no M-M bonding in this cluster, the Cu atoms do not obey the 16-electron rule, nor the 18-electron rule.…”