0000000000444984
AUTHOR
Jean-françois Halet
Electron‐Sponge Behavior, Reactivity and Electronic Structures of Cobalt‐Centered Cubic Co 9 Te 6 (CO) 8 Clusters (Eur. J. Inorg. Chem. 12/2008)
The cover picture shows an organometallic electron sponge and an elephant-ear sponge in the background (photo by F. and J. Burek, National Marine Sanctuaries). The electronic flexibility of the cobalt-centered cubic [Co9Te6(CO)8]n cluster ([3]n) in the central circle is expressed by differently charged states (n = 1+ to 5–). Starting from the upper left corner of our graphic in a clockwise direction, neutral [Co9Te6(CO)4(PPh3)4], structurally diverse networks of [Ph3PNPPh3][3] and [Ph3PNPPh3]2[3] salts and the core of the [Co9Te3{ν5-Cp′2Nb(CO)Te}3(CO)8] cluster as a pseudo-protonated representative of the [3]3– anion are shown. Details of the structural, electrochemical and theoretical prop…
Electron-Sponge Behavior and Electronic Structures in Cobalt-Centered Pentagonal Prismatic Co11Te7(CO)10 and Co11Te5(CO)15 Cluster Anions
The novel cluster anion [Co11Te5(CO)15]- ([3]-) has been isolated and structurally characterized as part of the salt [Cp*2Nb(CO)2][3] (Cp* = C5Me5). The cobalt-centered Co10 pentagonal prism is surrounded by a shell of two μ5-Te, three μ4-Te ligands, and 15 CO groups in terminal, symmetrical, and σ-semibridging bonding modes. The hybrid carbonyl-telluride character of the ligand shell is reflected in the solid state by a one-dimensional assembly of polyhedral prisms along a backbone of [Cp*2Nb(CO)2]+ cations. Electrochemical studies reveal the presence of four redox couples of [3]n (n = −1 to −5). The electronic structures of various metal-centered and empty pentagonal-prismatic (PP) M10 cl…
Electron-Sponge Behavior, Reactivity and Electronic Structures of Cobalt-Centered Cubic Co9Te6(CO)8 Clusters
Extended investigations of the reaction sequence [Cp′2Nb(Te2)H]/CH3Li/[Co2(CO)8] (Cp′ = tBuC5H4) led to the identification of Lin[3] {3 = [Co9Te6(CO)8]; n = 1, 2} salts through their transformation with [PPN]Cl into [PPN]n[3] (PPN = Ph3PNPPh3). These compounds form in the solid state columnar ([PPN][3]) or undulated 2D ([PPN]2[3]) supramolecular networks. Electrochemical studies of [Cp*2Nb(CO)2][3] (Cp* = C5Me5) or [Na(THF)6][3] revealed the presence of the redox couples [3]–/[3]2–/[3]3–/[3]4–/[3]5– regardless of the nature of the cation, whereas in the anodic part oxidative degradation of the cluster takes place. This behavior is in agreement with the observation that [3]– containing salts…