Zusammenfassung
The novel cluster anion [Co11Te5(CO)(15)](-) ([3](-)) has been isolated and structurally characterized as part of the salt [Cp* Nb-2(CO)(2)][3] (Cp* = C5Me5). The cobalt-centered Co-10 pentagonal prism is surrounded by a shell of two mu(5)-Te, three mu(4)-Te ligands, and 15 CO groups in terminal, symmetrical, and sigma-semibridging bonding modes. The hybrid carbonyl-telluride character of the ...
Zusammenfassung
The novel cluster anion [Co11Te5(CO)(15)](-) ([3](-)) has been isolated and structurally characterized as part of the salt [Cp* Nb-2(CO)(2)][3] (Cp* = C5Me5). The cobalt-centered Co-10 pentagonal prism is surrounded by a shell of two mu(5)-Te, three mu(4)-Te ligands, and 15 CO groups in terminal, symmetrical, and sigma-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*Nb-2(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) M-10 clusters (M = Co, Ni) are calculated and compared to those of pentagonal-antiprismatic (PA) M-10 structures. Closed-shells of 152 and 156 metal valence electrons, respectively, are found to determine the electronic structures and chemical properties of these geometries. From these considerations, magnetic properties have been predicted. They have been verified for the [Co11Te7(CO)(10)](-) cluster anion, which exhibits a singlet triplet gap of 0.318 kcal/mol.
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