New Co and Ni Clusters with Se and PPh₃ as Ligands: [Co₄(μ₃‐Se)₄(PPh₃)₄], [Co₆(μ₃‐Se)₈(PPh₃)₆], [Co₉(μ₄‐Se)₃(μ₃‐Se)₈(PPh₃)₆], and [Ni₃₄(μ₅‐Se)₂(μ₄‐Se)₂₀(PPh₃)₁₀]

Abstract

Four novel clusters of Co or Ni, Se, and PPh3 have been obtained in good yields from [MCl2(PPh3)2] and Se(SiMe3)2 in toluene. In all four clusters, whose structures have been elucidated, the actual core is surrounded by a sheath of phenyl groups. The empirical formulas are given in the title; the structure of the nickel complex is to be seen on the cover page of this issue. The four complexes are 60e, 98e, 137e, and 448e species, respectively.–The longer known analogous reaction with S(SiMe3)2 gave other types of products.

Structural Chemistry of Giant Metal Based Supramolecules

“…To the best of our knowledge, the largest nickel sulfide and selenide clusters, consisting of {Ni 32 S 24 } and {Ni 34 Se 22 } cores, were reported by D. Fenske (Table ). , Notably, the central parts of nickel-chalcogenide cores according to the authors possess different disorder pattern and rather different structure (Figure ).…”

Hierarchical nanosheets built from superatomic clusters: properties, exfoliation and single-crystal-to-single-crystal intercalation

“…As intra-and intermolecular edge site Co/Co distances are prohibitively long for through-space magnetic exchange (>9 A), 52 we propose the antiferromagnetic coupling is mediated through the diamagnetic Co 6 Se 8 core. 53 Considering that the previously reported Re 5 OsSe 8 cluster core, diamagnetic and isostructural with Co 6 Se 8 , has been shown to prevent the magnetic interaction between surface bound S ¼ 54 Alternatively, the edge Co may interact with the core via intervalence charge transfer processes that may be enabled at low temperature.…”

Building Diatomic and Triatomic Superatom Molecules

“…Superatoms having neutral cores capped with phosphine ligands are typically synthesized so that each ligand coordinates to a metal atom to form, for example, M 6 E 8 (PR 3 ) 6 structures (M = Cr, Co, Mo, Rh; E = S, Se, Te). − Substitution reactions of these phosphines are difficult because the M–P bonds tend to display low chemical reactivity at moderate temperatures and indiscriminate reactions at higher temperatures; the latter thermal reactions typically yield solid-state products. , Moreover, the differentiation of one of the phosphines from another in a symmetrically substituted metal chalcogenide cluster is a vexing challenge.…”