Electron-Sponge Behavior and Electronic Structures in Cobalt-Centered Pentagonal Prismatic Co11Te7(CO)10 and Co11Te5(CO)15 Cluster Ani
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- 作者：Olivier Cador ; Hé ; lè ; ne Cattey ; Jean-Franç ; ois Halet ; Walter Meier ; Yves Mugnier ; Joachim Wachter ; Jean-Yves Saillard ; Bachir Zouchoune ; Manfred Zabel
- 刊名：Inorganic Chemistry
- 出版年：2007
- 出版时间：January 22, 2007
- 年：2007
- 卷：46
- 期：2
- 页码：501 - 509
- 全文大小：304K
- 年卷期：v.46,no.2(January 22, 2007)
- ISSN：1520-510X
文摘
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
5-Te, three 4-Te ligands, and 15 CO groups in terminal, symmetrical, and 
-semibridging bonding modes. Thehybrid carbonyl-telluride character of the ligand shell is reflected in the solid state by a one-dimensional assemblyof polyhedral prisms along a backbone of [Cp*2Nb(CO)2]+ cations. Electrochemical studies reveal the presence offour redox couples of [3]n (n = -1 to -5). The electronic structures of various metal-centered and empty pentagonal-prismatic (PP) M10 clusters (M = Co, Ni) are calculated and compared to those of pentagonal-antiprismatic (PA)M10 structures. Closed-shells of 152 and 156 metal valence electrons, respectively, are found to determine theelectronic structures and chemical properties of these geometries. From these considerations, magnetic propertieshave been predicted. They have been verified for the [Co11Te7(CO)10]- cluster anion, which exhibits a singlet-triplet gap of 0.318 kcal/mol.
5-Te, three 4-Te ligands, and 15 CO groups in terminal, symmetrical, and -semibridging bonding modes. Thehybrid carbonyl-telluride character of the ligand shell is reflected in the solid state by a one-dimensional assemblyof polyhedral prisms along a backbone of [Cp*2Nb(CO)2]+ cations. Electrochemical studies reveal the presence offour redox couples of [3]n (n = -1 to -5). The electronic structures of various metal-centered and empty pentagonal-prismatic (PP) M10 clusters (M = Co, Ni) are calculated and compared to those of pentagonal-antiprismatic (PA)M10 structures. Closed-shells of 152 and 156 metal valence electrons, respectively, are found to determine theelectronic structures and chemical properties of these geometries. From these considerations, magnetic propertieshave been predicted. They have been verified for the [Co11Te7(CO)10]- cluster anion, which exhibits a singlet-triplet gap of 0.318 kcal/mol.