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Issue 12, 2013
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A combined NMR/DFT study on the ion pair structure of [(PR12R2)Au(η2-3-hexyne)]BF4 complexes

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Abstract

The interionic structure of four gold(I) π-alkyne ion pairs, with general formula [(PR12R2)Au(η2-3-hexyne)]BF4 (R1 = R2 = tBu, 1a; R1 = tBu, R2 = o-diphenyl, 2a; R1 = R2 = 2,4,6-trimethoxyphenyl, 3a; R1 = R2 = 2,4-di-tert-butylphenoxy, 4a), was studied by 19F, 1H-HOESY NMR spectroscopy. In all the cases the anion locates mainly close to the alkyne, but the degree of specificity of location strongly depends on the P-ligand and it is high for ion pairs bearing poorly electron donating PR12R2 ligands (particularly, 4a) and low for ion pairs with strongly electron donating PR12R2 ones (such as 3a). This result is rationalized through relativistic DFT calculations, showing that the electronic properties of the P-ligand finely tune the charge accumulation on the alkyne and, consequently, its ability of attracting the anion.

Graphical abstract: A combined NMR/DFT study on the ion pair structure of [(PR12R2)Au(η2-3-hexyne)]BF4 complexes

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Publication details

The article was received on 26 Sep 2012, accepted on 24 Oct 2012 and first published on 25 Oct 2012


Article type: Paper
DOI: 10.1039/C2DT32260A
Citation: Dalton Trans., 2013,42, 4122-4131
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    A combined NMR/DFT study on the ion pair structure of [(PR12R2)Au(η2-3-hexyne)]BF4 complexes

    G. Ciancaleoni, L. Belpassi, F. Tarantelli, D. Zuccaccia and A. Macchioni, Dalton Trans., 2013, 42, 4122
    DOI: 10.1039/C2DT32260A

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