Institut für Anorganische Chemie und Strukturchemie II, Heinrich-Heine-Universität Düsseldorf, Universitätsstrasse 1, 40225, Düsseldorf, Germany.
Dalton Trans. 2010 Mar 14;39(10):2708-16. doi: 10.1039/b922720b. Epub 2010 Feb 4.
The caesium and tetraethylammonium salts of the 1-cyanocarba-closo-dodecaborate anions 1-NC-closo-1-CB(11)X(11) (X = H, F, Cl, Br, I) were synthesized from CsLi[closo-1-CB(11)X(11)] and phenylcyanate. All anions are stable against aqueous acids and bases, except for the fluorinated anion 1-NC-closo-1-CB(11)F(11) that immediately reacts with water. The Cs(+) and Et(4)N salts of the anions were characterized by IR, Raman and multinuclear NMR spectroscopy as well as by MALDI and ESI mass spectrometry. The thermal properties of the Cs[1-NC-closo-1-CB(11)X(11)] (X = H, Cl, Br, I) and of some of their tetraethylammonium salts were studied by differential scanning calorimetry. The crystal structures of [Et(4)N][1-NC-closo-1-CB(11)H(11)] and Cs[1-NC-closo-1-CB(11)Cl(11)] were determined and the discussion of the structural and spectroscopic properties is supported by density functional and (RI)-MP2 calculations. A first insight into the hydrolysis of the 1-NC-closo-1-CB(11)F(11) anion is presented and its reactions with water are compared to those of other undecafluorinated carba-closo-dodecaborate anions. The reduced hydrolytic stability of the 1-NC-closo-1-CB(11)F(11) anion in comparison to its homologues is related to differences in the carbon-boron and boron-boron bond lengths of the {closo-1-CB(11)} cage and to different partial charges of the cluster atoms.
[1-氰基-closo-1-碳硼烷十二硼阴离子]1-NC-closo-1-CB(11)X(11)（X = H、F、Cl、Br、I）的铯盐和四乙基铵盐是由 CsLi[closo-1-CB(11)X(11)]和苯甲氰酸合成的。所有的阴离子都能抵抗水的酸碱，除了氟化阴离子1-NC-closo-1-CB(11)F(11)，它会立即与水反应。阴离子的 Cs(+)和Et(4)N盐通过红外、拉曼和多核 NMR 光谱以及 MALDI 和 ESI 质谱进行了表征。通过差示扫描量热法研究了 Cs[1-NC-closo-1-CB(11)X(11)]（X = H、Cl、Br、I）及其一些四乙基铵盐的热性质。[Et(4)N][1-NC-closo-1-CB(11)H(11)]和 Cs[1-NC-closo-1-CB(11)Cl(11)]的晶体结构已被确定，并通过密度泛函和（RI）-MP2 计算支持了结构和光谱性质的讨论。初步探讨了1-NC-closo-1-CB(11)F(11)阴离子的水解，并将其与其他未氟化的 carba-closo-十二硼阴离子的水解反应进行了比较。与同系物相比，1-NC-closo-1-CB(11)F(11)阴离子水解稳定性的降低与{closo-1-CB(11)}笼的碳硼键和硼硼键长度的差异以及簇原子的不同部分电荷有关。
