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Issue 34, 2013
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Diarylhalotelluronium(IV) cations [(8-Me2NC10H6)2TeX]+ (X = Cl, Br, I) stabilized by intramolecularly coordinating N-donor substituents

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Abstract

The stoichiometrically controlled halogenation of the intramolecularly coordinated diaryltelluride (8-Me2NC10H6)2Te using SO2Cl2, Br2 and I2 was studied. At an equimolar ratio, the diarylhalotelluronium cations [(8-Me2NC10H6)2TeX]+ (1, X = Cl; 2, X = Br; 3, X = I) formed and were isolated as 1·Cl·H2O·1/2THF, 2·Br, and 3·I, respectively. When the same reactions were carried out in the presence of KPF6, 1·PF6 and 22·Br·PF6 were obtained. The chlorination of (8-Me2NC10H6)2Te with an excess of SO2Cl2 occurred with a double electrophilic substitution at the 8-dimethylaminonaphthyl residues (in the ortho- and para-positions) and afforded the diaryltellurium dichloride (5,7-Cl2-8-Me2NC10H4)2TeCl2 (4). The bromination of (8-Me2NC10H6)2Te with three equivalents of Br2 took place with a single electrophilic substitution at the 8-dimethylaminonaphthyl residues (in the para-positions) and provided the diaryltellurium dibromide (5-Br-8-Me2NC10H5)2TeBr2 (5), while an excess of Br2 produced the diarylbromotelluronium cation [(5-Br-8-Me2NC10H5)2TeBr]+ (6) that was isolated as 6·Br3. The reaction of (8-Me2NC10H6)2Te with two or three equivalents of iodine provided 3·I3 and 3·I3·I2, respectively. In the presence of water, 1·Cl·H2O·1/2THF, 2·Br, 3·I and 3·I3 hydrolyzed to give the previously known diarylhydroxytelluronium cation [(8-Me2NC10H6)2TeOH]+ (7) that was isolated as 7·Cl, 7·Br·H2O·THF, 7·I and 7·I3·H2O, respectively. The molecular structures of 1–7 were investigated in the solid-state by 125Te MAS NMR spectroscopy and X-ray crystallography and in solution by multinuclear NMR spectroscopy (1H, 13C, 125Te), electrospray mass spectrometry and conductivity measurements. The stabilization of cations 1–3 by the intramolecular coordination was estimated by DFT calculations at the B3PW91/TZ level of theory.

Graphical abstract: Diarylhalotelluronium(iv) cations [(8-Me2NC10H6)2TeX]+ (X = Cl, Br, I) stabilized by intramolecularly coordinating N-donor substituents

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Publication details

The article was received on 17 Apr 2013, accepted on 18 Jun 2013 and first published on 19 Jun 2013


Article type: Paper
DOI: 10.1039/C3DT51011E
Citation: Dalton Trans., 2013,42, 12193-12202
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    Diarylhalotelluronium(IV) cations [(8-Me2NC10H6)2TeX]+ (X = Cl, Br, I) stabilized by intramolecularly coordinating N-donor substituents

    J. Beckmann, J. Bolsinger, A. Duthie and P. Finke, Dalton Trans., 2013, 42, 12193
    DOI: 10.1039/C3DT51011E

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