The effect of counter ions on the far-infrared spectra of tris (triphenylphosphinegold) oxonium dimer salts

Trystan Bennett; Alexander Falcinella; Reuben White; Rohul Adnan; Vladimir Golovko; Gunther Andersson; Gregory Metha

doi:10.1039/c5ra11599j

The effect of counter ions on the far-infrared spectra of tris (triphenylphosphinegold) oxonium dimer salts

Trystan Bennett, Alexander Falcinella, Reuben White, Rohul Adnan, Vladimir Golovko, Gunther Andersson, Gregory Metha

Research output: Contribution to journal › Article › peer-review

1 Citation (Scopus)

Abstract

Two tris(triphenylphosphinegold)oxonium dimer salts [{{Au(PPh₃)}₃(μ₃-O)}₂]²⁺(X^-)₂ (X = BF-4, MnO-4) were investigated via synchrotron-based far-infrared vibrational spectroscopy and density functional theory modelled at the M06/LANL2DZ level of theory. The 50-800 cm^-1 region of both oxonium salts is presented, with the spectrum for [{{Au(PPh₃)}₃(μ₃-O)}₂]²⁺(BF-4)₂ found to possess a large feature at 330.3 cm^-1, attributable to counter-ion vibrational modes, which is only predicted upon explicit inclusion of counter-ions in the calculation. A feature around 107 cm^-1 observed for the [{{Au(PPh₃)}₃(μ₃-O)}₂]²⁺(BF-4)₂ infrared spectrum is assigned to 21 distinct vibrational modes arising from Au-Au bond stretching and other motions of the Au core. The same feature is predicted to be present within the [{{Au(PPh₃)}₃(μ₃-O)}₂]²⁺(MnO-4)₂ spectrum but is masked by experimental noise. In the 50-400 cm^-1 region, the relative intensities of predicted vibrational modes is found to depend heavily on the presence and nature of the counter-ions, while within the 400-800 cm^-1 region, little dependence of the theoretical spectra on the type of counter-ion is predicted. Finally, the dimerization energies of both [{{Au(PPh₃)}₃(μ₃-O)}₂]²⁺(BF-4)₂ and [{{Au(PPh₃)}₃(μ₃-O)}₂]²⁺(MnO-4)₂ are calculated to be 3.06 eV and 3.20 eV, respectively, when the counter-ions are explicitly included within the calculation, and just 1.10 eV in their absence.

Original language	English
Pages (from-to)	74499-74505
Number of pages	7
Journal	RSC Advances
Volume	5
Issue number	91
DOIs	https://doi.org/10.1039/c5ra11599j
Publication status	Published - 2015

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@article{d03b6515feb34fea9e6d7e3d66546925,

title = "The effect of counter ions on the far-infrared spectra of tris (triphenylphosphinegold) oxonium dimer salts",

abstract = "Two tris(triphenylphosphinegold)oxonium dimer salts [{{Au(PPh3)}3(μ3-O)}2]2+(X-)2 (X = BF-4, MnO-4) were investigated via synchrotron-based far-infrared vibrational spectroscopy and density functional theory modelled at the M06/LANL2DZ level of theory. The 50-800 cm-1 region of both oxonium salts is presented, with the spectrum for [{{Au(PPh3)}3(μ3-O)}2]2+(BF-4)2 found to possess a large feature at 330.3 cm-1, attributable to counter-ion vibrational modes, which is only predicted upon explicit inclusion of counter-ions in the calculation. A feature around 107 cm-1 observed for the [{{Au(PPh3)}3(μ3-O)}2]2+(BF-4)2 infrared spectrum is assigned to 21 distinct vibrational modes arising from Au-Au bond stretching and other motions of the Au core. The same feature is predicted to be present within the [{{Au(PPh3)}3(μ3-O)}2]2+(MnO-4)2 spectrum but is masked by experimental noise. In the 50-400 cm-1 region, the relative intensities of predicted vibrational modes is found to depend heavily on the presence and nature of the counter-ions, while within the 400-800 cm-1 region, little dependence of the theoretical spectra on the type of counter-ion is predicted. Finally, the dimerization energies of both [{{Au(PPh3)}3(μ3-O)}2]2+(BF-4)2 and [{{Au(PPh3)}3(μ3-O)}2]2+(MnO-4)2 are calculated to be 3.06 eV and 3.20 eV, respectively, when the counter-ions are explicitly included within the calculation, and just 1.10 eV in their absence.",

author = "Trystan Bennett and Alexander Falcinella and Reuben White and Rohul Adnan and Vladimir Golovko and Gunther Andersson and Gregory Metha",

year = "2015",

doi = "10.1039/c5ra11599j",

language = "English",

volume = "5",

pages = "74499--74505",

journal = "RSC Advances",

issn = "2046-2069",

publisher = "Royal Society of Chemistry",

number = "91",

}

TY - JOUR

T1 - The effect of counter ions on the far-infrared spectra of tris (triphenylphosphinegold) oxonium dimer salts

AU - Bennett, Trystan

AU - Falcinella, Alexander

AU - White, Reuben

AU - Adnan, Rohul

AU - Golovko, Vladimir

AU - Andersson, Gunther

AU - Metha, Gregory

PY - 2015

Y1 - 2015

N2 - Two tris(triphenylphosphinegold)oxonium dimer salts [{{Au(PPh3)}3(μ3-O)}2]2+(X-)2 (X = BF-4, MnO-4) were investigated via synchrotron-based far-infrared vibrational spectroscopy and density functional theory modelled at the M06/LANL2DZ level of theory. The 50-800 cm-1 region of both oxonium salts is presented, with the spectrum for [{{Au(PPh3)}3(μ3-O)}2]2+(BF-4)2 found to possess a large feature at 330.3 cm-1, attributable to counter-ion vibrational modes, which is only predicted upon explicit inclusion of counter-ions in the calculation. A feature around 107 cm-1 observed for the [{{Au(PPh3)}3(μ3-O)}2]2+(BF-4)2 infrared spectrum is assigned to 21 distinct vibrational modes arising from Au-Au bond stretching and other motions of the Au core. The same feature is predicted to be present within the [{{Au(PPh3)}3(μ3-O)}2]2+(MnO-4)2 spectrum but is masked by experimental noise. In the 50-400 cm-1 region, the relative intensities of predicted vibrational modes is found to depend heavily on the presence and nature of the counter-ions, while within the 400-800 cm-1 region, little dependence of the theoretical spectra on the type of counter-ion is predicted. Finally, the dimerization energies of both [{{Au(PPh3)}3(μ3-O)}2]2+(BF-4)2 and [{{Au(PPh3)}3(μ3-O)}2]2+(MnO-4)2 are calculated to be 3.06 eV and 3.20 eV, respectively, when the counter-ions are explicitly included within the calculation, and just 1.10 eV in their absence.

AB - Two tris(triphenylphosphinegold)oxonium dimer salts [{{Au(PPh3)}3(μ3-O)}2]2+(X-)2 (X = BF-4, MnO-4) were investigated via synchrotron-based far-infrared vibrational spectroscopy and density functional theory modelled at the M06/LANL2DZ level of theory. The 50-800 cm-1 region of both oxonium salts is presented, with the spectrum for [{{Au(PPh3)}3(μ3-O)}2]2+(BF-4)2 found to possess a large feature at 330.3 cm-1, attributable to counter-ion vibrational modes, which is only predicted upon explicit inclusion of counter-ions in the calculation. A feature around 107 cm-1 observed for the [{{Au(PPh3)}3(μ3-O)}2]2+(BF-4)2 infrared spectrum is assigned to 21 distinct vibrational modes arising from Au-Au bond stretching and other motions of the Au core. The same feature is predicted to be present within the [{{Au(PPh3)}3(μ3-O)}2]2+(MnO-4)2 spectrum but is masked by experimental noise. In the 50-400 cm-1 region, the relative intensities of predicted vibrational modes is found to depend heavily on the presence and nature of the counter-ions, while within the 400-800 cm-1 region, little dependence of the theoretical spectra on the type of counter-ion is predicted. Finally, the dimerization energies of both [{{Au(PPh3)}3(μ3-O)}2]2+(BF-4)2 and [{{Au(PPh3)}3(μ3-O)}2]2+(MnO-4)2 are calculated to be 3.06 eV and 3.20 eV, respectively, when the counter-ions are explicitly included within the calculation, and just 1.10 eV in their absence.

U2 - 10.1039/c5ra11599j

DO - 10.1039/c5ra11599j

M3 - Article

VL - 5

SP - 74499

EP - 74505

JO - RSC Advances

JF - RSC Advances

SN - 2046-2069

IS - 91

ER -