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首页> 外文期刊>Journal of mass spectrometry: JMS >Gas-phase chemistry of ionized and protonated GeF_4: A joint experimental and theoretical study
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Gas-phase chemistry of ionized and protonated GeF_4: A joint experimental and theoretical study

机译：电离和质子化的GeF_4的气相化学：联合实验和理论研究

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The gas-phase ion chemistry of GeF_4 and of its mixtures with water, ammonia and hydrocarbons was investigated by ion trap mass spectrometry (ITMS) and ab initio calculations. Under ITMS conditions, the only fragment detected from ionized GeF_4 is GeF_3~+. This cation is a strong Lewis acid, able to react with H_2O, NH3_ and the unsaturated C_2H_2, C_2H_4 and C_6H_6 by addition-HF elimination reactions to form F _2Ge(XH)~+, FGe(XH)~2+, Ge(XH) _3~+ (X = OH or NH_2), F_2GeC _2H~+, F_2GeC_2H_3~+ and F_2GeC_6H_5~+. The structure, stability and thermochemistry of these products and the mechanistic aspects of the exemplary reactions of GeF_3~+ with H_2O, NH_3 and C_6H_6 were investigated by MP_2 and coupled cluster calculations. The experimental proton affinity (PA) and gas basicity (GB) of GeF_4 were estimated as 121.5 ± 6.0 and 117.1 ± 6.0 kcal mol-1, respectively, and GeF4H + was theoretically characterized as an ion-dipole complex between GeF_3~+ and HF. Consistently, it reacts with simple inorganic and organic molecules to form GeF_3~+-L complexes (L = H2O, NH3, C_2H_2, C _2H_4, C_6H_6, CO2, SO 2 and GeF4). The theoretical investigation of the stability of these ions with respect to GeF3+ and L disclosed nearly linear correlations between their dissociation enthalpies and free energies and the PA and GB of L. Comparing the behavior of GeF _3~+ with the previously investigated CF_3~+ and SiF_3~+ revealed a periodically reversed order of reactivity CF_3~+ < GeF_3~+ < SiF_3~+. This parallels the order of the Lewis acidities of the three cations.
机译：通过离子阱质谱（ITMS）和从头算计算研究了GeF_4及其与水，氨和碳氢化合物的混合物的气相离子化学。在ITMS条件下，从电离的GeF_4中检测到的唯一片段是GeF_3〜+。该阳离子为强路易斯酸，可通过加氢消除反应与H_2O，NH3_和不饱和C_2H_2，C_2H_4和C_6H_6反应，形成F _2Ge（XH）〜+，FGe（XH）〜2 +，Ge（XH ）_3〜+（X = OH或NH_2），F_2GeC _2H〜+，F_2GeC_2H_3〜+和F_2GeC_6H_5〜+。通过MP_2和耦合聚类计算研究了这些产物的结构，稳定性和热化学性质，以及GeF_3〜+与H_2O，NH_3和C_6H_6的反应机理。 GeF_4的实验质子亲和力（PA）和气体碱度（GB）分别估计为121.5±6.0和117.1±6.0 kcal mol-1，并且GeF4H +在理论上被表征为GeF_3〜+与HF之间的离子偶极复合物。一致地，它与简单的无机和有机分子反应形成GeF_3〜+ -L配合物（L = H2O，NH3，C_2H_2，C _2H_4，C_6H_6，CO2，SO 2和GeF4）。这些离子相对于GeF3 +和L的稳定性的理论研究揭示了其离解焓和自由能与L的PA和GB之间的线性关系。将GeF _3〜+的行为与先前研究的CF_3〜+和SiF_3〜+显示出反应性CF_3〜+

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