2015 |
Mendizabal, F; Miranda-Rojas, S; Barrientos-Poblete, L Theoretical Study on Interactions of Fluorinated Organomercurials with Arene and Gold Fragments Artículo de revista Physical Chemistry Chemical Physics, 17 (39), pp. 26417-26428, 2015, ISSN: 1463-9076. Resumen | Enlaces | BibTeX | Etiquetas: attraction, au-i, chemistry, closed-shell complexation, coordination, energies, hg-ii, mercury @article{RN253, title = {Theoretical Study on Interactions of Fluorinated Organomercurials with Arene and Gold Fragments}, author = { F. Mendizabal and S. Miranda-Rojas and L. Barrientos-Poblete}, url = {/brokenurl#<Go to ISI>://WOS:000362291300083}, doi = {10.1039/c5cp04503g}, issn = {1463-9076}, year = {2015}, date = {2015-01-01}, journal = {Physical Chemistry Chemical Physics}, volume = {17}, number = {39}, pages = {26417-26428}, abstract = {The electronic structure and spectroscopic properties of [Hg(C6F5)(2)](2)-(L); [Hg-3(o-C6F4)(3)](2)center dotL (L = naphthalene, biphenyl, fluorene) and [Hg-3(o-C6F4)(3)]Au-3(mu-C(OEt)=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 [Hg-3(o-C6F4)(3)](2)center dotL 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 [Hg-3(o-C6F4)(3)]Au-3(mu-C(OEt)=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] Au-3(mu-C(OEt)=NC6H4CH3)(3) model. The same trend is maintained for the [Hg-3(o-C6F4)(3)]Au-3(mu-C(OEt)=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.}, keywords = {attraction, au-i, chemistry, closed-shell complexation, coordination, energies, hg-ii, mercury}, pubstate = {published}, tppubtype = {article} } The electronic structure and spectroscopic properties of [Hg(C6F5)(2)](2)-(L); [Hg-3(o-C6F4)(3)](2)center dotL (L = naphthalene, biphenyl, fluorene) and [Hg-3(o-C6F4)(3)]Au-3(mu-C(OEt)=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 [Hg-3(o-C6F4)(3)](2)center dotL 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 [Hg-3(o-C6F4)(3)]Au-3(mu-C(OEt)=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] Au-3(mu-C(OEt)=NC6H4CH3)(3) model. The same trend is maintained for the [Hg-3(o-C6F4)(3)]Au-3(mu-C(OEt)=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. |
2015 |
Theoretical Study on Interactions of Fluorinated Organomercurials with Arene and Gold Fragments Artículo de revista Physical Chemistry Chemical Physics, 17 (39), pp. 26417-26428, 2015, ISSN: 1463-9076. |