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Issue 8, 2006
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New route to 1-thia-closo-dodecaborane(11), closo-1-SB11H11, and its halogenation reactions. The effect of the halogen on the dipole moments and the NMR spectra and the importance of spin–orbit coupling for the 11B chemical shifts

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Abstract

Reaction between nido-B10H14 (1) and elemental sulfur in CHCl3 in the presence of Et3N at room temperature, followed by treatment with Et3N·BH3 at 170–190 °C, resulted in the isolation of closo-1-SB11H11 (2) in 50% yield. Selected electrophilic halogenation reactions of compound 2 led to the isolation of a series of monohalogenated derivatives of general constitution 12-X-closo-1-SB11H10 (12-X-2, where X = Cl, Br, and I). The structures of 12-Cl-2 and 12-I-2 were determined by an X-ray diffraction analysis and the structures of all compounds were geometry optimised at the RMP2(fc)/6-31G* level. The constitution of all compounds is consistent with the results of mass spectrometry and multinuclear (1H and 11B) spectroscopy complemented by two-dimensional [11B–11B]-COSY and 1H{11B(selective)} NMR measurements. Experimental 11B chemical shifts generally show acceptable agreement with theoretical values calculated by GIAO methods, but spin–orbit coupling must be included for nuclei bearing heavy-atom substituents such as Br or I. The dipole moments determined for the B12-X bonds show similarities to those of aliphatic C–X bonds and confirm unambiguously the B12 → S dipole moment orientation in the SB11 cage.

Graphical abstract: New route to 1-thia-closo-dodecaborane(11), closo-1-SB11H11, and its halogenation reactions. The effect of the halogen on the dipole moments and the NMR spectra and the importance of spin–orbit coupling for the 11B chemical shifts

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Publication details

The article was received on 31 Aug 2005, accepted on 28 Oct 2005 and first published on 25 Nov 2005


Article type: Paper
DOI: 10.1039/B512345C
Citation: Dalton Trans., 2006,0, 1024-1029

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    New route to 1-thia-closo-dodecaborane(11), closo-1-SB11H11, and its halogenation reactions. The effect of the halogen on the dipole moments and the NMR spectra and the importance of spin–orbit coupling for the 11B chemical shifts

    J. Macháček, J. Plešek, J. Holub, D. Hnyk, V. Všetečka, I. Císařová, M. Kaupp and B. Štíbr, Dalton Trans., 2006, 0, 1024
    DOI: 10.1039/B512345C

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