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Issue 10, 2010
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Salts of the 1-cyanocarba-closo-dodecaborate anions [1-NC-closo-1-CB11X11] (X = H, F, Cl, Br, I)

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Abstract

The caesium and tetraethylammonium salts of the 1-cyanocarba-closo-dodecaborate anions [1-NC-closo-1-CB11X11] (X = H, F, Cl, Br, I) were synthesized from CsLi[closo-1-CB11X11] and phenylcyanate. All anions are stable against aqueous acids and bases, except for the fluorinated anion [1-NC-closo-1-CB11F11] that immediately reacts with water. The Cs+ and [Et4N]+ 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-CB11X11] (X = H, Cl, Br, I) and of some of their tetraethylammonium salts were studied by differential scanning calorimetry. The crystal structures of [Et4N][1-NC-closo-1-CB11H11] and Cs[1-NC-closo-1-CB11Cl11] 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-CB11F11] 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-CB11F11] anion in comparison to its homologues is related to differences in the carbonboron and boronboron bond lengths of the {closo-1-CB11} cage and to different partial charges of the cluster atoms.

Graphical abstract: Salts of the 1-cyanocarba-closo-dodecaborate anions [1-NC-closo-1-CB11X11]− (X = H, F, Cl, Br, I)

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Publication details

The article was received on 30 Oct 2009, accepted on 06 Jan 2010 and first published on 04 Feb 2010


Article type: Paper
DOI: 10.1039/B922720B
Citation: Dalton Trans., 2010,39, 2708-2716
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    Salts of the 1-cyanocarba-closo-dodecaborate anions [1-NC-closo-1-CB11X11] (X = H, F, Cl, Br, I)

    M. Finze, J. A. P. Sprenger and B. B. Schaack, Dalton Trans., 2010, 39, 2708
    DOI: 10.1039/B922720B

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