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Issue 39, 2015
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Theoretical study on interactions of fluorinated organomercurials with arene and gold fragments

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Abstract

The electronic structure and spectroscopic properties of [Hg(C6F5)2]2–{L}, [Hg3(o-C6F4)3]2·{L} (L = naphthalene, biphenyl, fluorene) and [Hg3(o-C6F4)3]{Au3(μ-C(OEt)[double bond, length as m-dash]NC6H4CH3)3}n (n = 1, 2) adducts were studied at the HF, MP2, SCS-MP2, DFT and DFT-D3 levels. The intermolecular interactions among the fragments were analyzed using the levels of calculations proposed. The energy decomposition analysis at the TPSS-D3 level was used to define the dominant components of the interaction. The van der Waals interactions between mercury and arene (Hg–arene) were found to be the main short-range stability contribution in the [Hg(C6F5)2]2–{L} and [Hg3(o-C6F4)3]2·{L} complexes. At the MP2, SCS-MP2 and DFT-D3 levels, equilibrium Hg–C distances are between 360 and 310 pm. The pair-wise energies were found to be between 18.0 and 6.0 kJ mol−1. In the [Hg3(o-C6F4)3]{Au3(μ-C(OEt)[double bond, length as m-dash]NC6H4CH3)3}n (n = 1, 2) complexes the metallophilic intermolecular interaction is Hg–Au. Pair-wise energies of 85.7, 39.4, 78.1 and 57.9 kJ mol−1 were found at the MP2, SCS-MP2, TPSS-D3 and PBE-D3 levels using the [Hg3(o-C6F4)3]{Au3(μ-C(OEt)[double bond, length as m-dash]NC6H4CH3)3} model. The same trend is maintained for the [Hg3(o-C6F4)3]{Au3(μ-C(OEt)[double bond, length as m-dash]NC6H4CH3)3}2 model: 73.4, 29.3, 70.6 and 61.3 kJ mol−1 by MP2, SCS-MP2, TPSS-D3 and PBE-D3, respectively. The absorption spectra of these complexes were calculated using the single excitation time-dependent method at the TPSS-D3 level to validate the models against the experimental data.

Graphical abstract: Theoretical study on interactions of fluorinated organomercurials with arene and gold fragments

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Publication details

The article was received on 30 Jul 2015, accepted on 11 Sep 2015 and first published on 14 Sep 2015


Article type: Paper
DOI: 10.1039/C5CP04503G
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Citation: Phys. Chem. Chem. Phys., 2015,17, 26417-26428
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    Theoretical study on interactions of fluorinated organomercurials with arene and gold fragments

    F. Mendizabal, S. Miranda-Rojas and L. Barrientos, Phys. Chem. Chem. Phys., 2015, 17, 26417
    DOI: 10.1039/C5CP04503G

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