Weakly coordinating nature of a carborane cage bearing different halogen atoms. Synthesis and structural characterization of icosahedral mixed halocarborane anions, 1-H-CB11Y5X6- (X, Y = Cl, Br, I)

C. W. Tsang, Q. Yang, E. T.P. Sze, T. C.W. Mak, D. T.W. Chan, Z. Xie

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Abstract

Mixed halocarborane anions, 1-H-CB11Y5X6- (X, Y = Cl, Br, I), have been prepared by treatment of [Me3NH]-[1-H-CB11H5X6] (X = Cl, Br, I) with proper halogenating reagents at 180-220 °C in a sealed tube in high yield. These new anions are fully characterized by 1H, 13C, and 11B NMR, IR, and negative-ion MALDI MS spectroscopy. Some are further confirmed by single-crystal X-ray analyses. The weakly coordinating nature of these anions is probed by 29Si chemical shifts of the resulting Pri3Si(1-H-CB11Y5X6) compounds. The results suggest that the coordinating ability of these anions is mainly dependent on the substituents at 7-12 positions (namely, X atoms), and the contribution from the upper belt substituents Y is relatively small. These suggestions are consistent with the results obtained from the structural study of silver salts of mixed halo- and perhalocarborane anions.

Original languageEnglish
Pages (from-to)5851-5858
Number of pages8
JournalInorganic Chemistry
Volume39
Issue number25
DOIs
Publication statusPublished - 11 Dec 2000
Externally publishedYes

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