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Experimental and Theoretical Study on the Gas-Phase Reactions of Germyl Radicals with NF3: Homolytic Substitution at the Nitrogen Atom vs Fluorine Abstraction
ACS Omega ( IF 3.7 ) Pub Date : 2020-03-03 , DOI: 10.1021/acsomega.9b03729
Paola Antoniotti 1, 2 , Paola Benzi 1, 2 , Domenica Marabello 1, 2 , Daniele Rosso 1
ACS Omega ( IF 3.7 ) Pub Date : 2020-03-03 , DOI: 10.1021/acsomega.9b03729
Paola Antoniotti 1, 2 , Paola Benzi 1, 2 , Domenica Marabello 1, 2 , Daniele Rosso 1
Affiliation
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In this paper, we report on the unexplored reaction mechanisms of bimolecular homolytic substitution (SH2) between GeH3 radicals and the nitrogen atom of NF3. The SH2 reactions are studied both experimentally and theoretically with ab initio and density functional theory (DFT) calculations. The experimental results of X-ray irradiation of mixtures of GeH4 and NF3 show the formation of GeH3–NF2 and GeH3–F. The trend of product yields as a function of the increase in GeH4 partial pressure in the irradiated mixtures evidences the predominant role of GeH3 radicals. Particularly, the SH2 mechanism can be hypothesized for the reaction between GeH3 radicals and NF3 molecules leading to GeH3–NF2. This mechanism is further confirmed by the increase in GeH3–NF2 yield observed if O2 is added, as a radical scavenger, to the reaction mixture. In agreement with the experimental data, from the calculations performed at the CCSD(T) and G3B3 levels of theory, we observe that the GeH3–NF2 product actually occurs from a bimolecular homolytic substitution by the GeH3 radical, which attacks the N atom of NF3, and this reaction is in competition with the fluorine abstraction reaction leading to GeH3F, even if other mechanisms may be involved in the formation of this product.
中文翻译:
胚芽自由基与NF 3气相反应的实验和理论研究:氮原子与氟提取的均质取代
在本文中,我们报道了GeH 3自由基和NF 3的氮原子之间双分子均溶取代(S H 2)的未探索的反应机理。通过从头算和密度泛函理论(DFT)计算,对S H 2反应进行了实验和理论研究。对GeH 4和NF 3的混合物进行X射线辐照的实验结果表明,形成了GeH 3 -NF 2和GeH 3 -F。产物产率随辐照混合物中GeH 4分压的增加而变化的趋势证明了GeH 3的主要作用部首。尤其是,可以假设S H 2的机理是GeH 3自由基与NF 3分子之间导致GeH 3 -NF 2的反应。如果将O 2作为自由基清除剂添加到反应混合物中,则观察到的GeH 3 -NF 2产率增加进一步证实了该机理。与实验数据相一致,从在CCSD(T)和G3B3理论水平上进行的计算,我们观察到GeH 3 -NF 2产物实际上是由GeH 3自由基的双分子均溶取代产生的,该自由基攻击N NF 3的原子,并且该反应与导致GeH 3 F的氟提取反应竞争,即使该产物的形成可能涉及其他机理。
更新日期:2020-03-19
中文翻译:
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胚芽自由基与NF 3气相反应的实验和理论研究:氮原子与氟提取的均质取代
在本文中,我们报道了GeH 3自由基和NF 3的氮原子之间双分子均溶取代(S H 2)的未探索的反应机理。通过从头算和密度泛函理论(DFT)计算,对S H 2反应进行了实验和理论研究。对GeH 4和NF 3的混合物进行X射线辐照的实验结果表明,形成了GeH 3 -NF 2和GeH 3 -F。产物产率随辐照混合物中GeH 4分压的增加而变化的趋势证明了GeH 3的主要作用部首。尤其是,可以假设S H 2的机理是GeH 3自由基与NF 3分子之间导致GeH 3 -NF 2的反应。如果将O 2作为自由基清除剂添加到反应混合物中,则观察到的GeH 3 -NF 2产率增加进一步证实了该机理。与实验数据相一致,从在CCSD(T)和G3B3理论水平上进行的计算,我们观察到GeH 3 -NF 2产物实际上是由GeH 3自由基的双分子均溶取代产生的,该自由基攻击N NF 3的原子,并且该反应与导致GeH 3 F的氟提取反应竞争,即使该产物的形成可能涉及其他机理。