Journal
INORGANIC CHEMISTRY
Volume 54, Issue 4, Pages 1965-1973Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ic502866h
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Funding
- Research Grants Council of the Hong Kong Special Administration Region [CUHK7/CRF/12G, 14306114]
- National Basic Research Program of China (973 Program) [2012CB821600]
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The synthesis, structure, spectroscopic characterization, and density functional theory (DFT) calculations of several 13-vertex carborane radical anions were described. Reactions of 13-vertex closo-carboranes with 1 equiv of finely cut sodium metal in tetrahydrofuran at room temperature afforded the corresponding sodium salts of carborane radical anions as dark-red crystals in very good yield. They represent a rare class of clusters having 2n + 3 framework electrons, which lie between the two well-established and abundant closed 2n + 2 (closo) and open 2n + 4 (nido) skeleton systems. However, attempts to prepare the 12- or 14-vertex analogues failed. DFT calculations indicate that the Delta G(sol,1) Delta G(sol,2) values, the difference in the solvation-corrected free-energy changes between the first and second one-electron-reduction processes, can be used as a measure for the stability of carborane radical anions. The relatively high stability of 13-vertex carborane radical anions is related to the unique structures of 13-vertex carboranes, which give rise to minimal structure disruption upon the first one-electron reduction.
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