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首页> 外文期刊>RSC Advances >The effect of counter ions on the far-infrared spectra of tris(triphenylphosphinegold)oxonium dimer salts
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The effect of counter ions on the far-infrared spectra of tris(triphenylphosphinegold)oxonium dimer salts

机译：抗衡离子对三（三苯基膦）的氧铵二聚盐远红外光谱的影响

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Two tris(triphenylphosphinegold)oxonium dimer salts [{{Au(PPh _(3) )} _(3) (μ _(3) ?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(PPh _(3) )} _(3) (μ _(3) ?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(PPh _(3) )} _(3) (μ _(3) ?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(PPh _(3) )} _(3) (μ _(3) ?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(PPh _(3) )} _(3) (μ _(3) ?O)} _(2) ] ~(2+) (BF ~(?) _(4) ) _(2) and [{{Au(PPh _(3) )} _(3) (μ _(3) ?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.
机译：两个三（三苯基膦）恶壬二聚体盐[{{Au（PPH _（3））} _（3）（μ_（3）ΔO）} _（2）]〜（2+）（x〜（？） ）_（2）（x = bf〜（？）_（4），通过在M06 / LANL2DZ水平上建模的基于同步的远红外振动光谱和密度泛函理论来研究MnO〜（α）_（4））理论。呈现了两种氧化鎓盐的50-800cm〜（α1）区域，其中频谱为[{{au（pph _（pph _（3））} _（3）（μ_（3）ΔO）} _（ 2）]〜（2+）（bf〜（Δ）_（4））_（2）发现在330.3cm〜（？1）中具有大的特征，可归因于抵抗离子振动模式，这仅预测在计算计算中明确包含反离子。为[{{Au（PPH _（3））} _（3）（μ_（3）α）} _（2）]〜（2+）（3）（ BF〜（？）_（4））_（2）红外光谱被分配到来自Au-au键拉伸和Au芯的其他运动产生的21种不同的振动模式。预计存在相同的特征存在于[{{au（pph _（3））}} _（3）（μ_（3）ΔO）} _（2）]〜（2+）（MnO〜（ ？）_（4））_（2）光谱但是通过实验噪声掩盖。在50-400cm〜（？1）区域中，发现预测的振动模式的相对强度依赖于对抗离子的存在和性质，而在400-800cm〜（？1）区域内，预测了理论光谱对反离子类型的几乎没有依赖性。最后，{{au（pph _（3））}} _（3）（μ_（3）Δo）}} _（2）]〜（bf〜（？）_ （4））_（2）和[{{au（pph _（3））} _（3）（μ_（3）ΔO）} _（2）]〜（2+）（mno〜（？ ）_（4））_（2）分别计算为3.06eV和3.20eV，当反离子明确地包括在计算中，并且在缺席的情况下只有1.10个EV。

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