Quantitative Aspects of Gas-Phase Metal Ion Chemistry: Conservation of Spin, Participation of f Orbitals, and C–H Activation and C–C Coupling
Quantitative Aspects of Gas-Phase Metal Ion Chemistry: Conservation of Spin, Participation of f Orbitals, and C–H Activation and C–C Coupling
复制标题
气相金属离子化学的定量方面：自旋守恒、f 轨道参与、C–H 激活和 C–C 偶联
DOI：
10.1021/acs.jpca.3c06023
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Armentrout, P. B.
中科院分区：
文献类型：
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作者：
Armentrout, P. B.
在这篇专题文章中，我回顾了40多年来在整个元素周期表中涉及原子金属阳离子及其团簇的引导离子束串联质谱学(GIBMS)研究。考虑了自旋守恒(或缺乏自旋守恒)作用的研究是主要关注的焦点，并对所考察的影响进行了定量评估。指出有必要对较重元素进行具体国家的研究，以及对反应性中的自旋-轨道相互作用进行更定量的评估。由于GIBMS实验明确地评估了大范围内反应的动能依赖性，因此突出了几个有趣和不同寻常的观察结果。对这种不寻常的反应事件进行更详细的研究将是受欢迎的。综述了C-H键的活化和随之而来的C-C偶联事件，并鼓励了未来的工作。最后，考察了镧系元素和吖系元素的研究，旨在了解f轨道在化学中的作用，它们既是成键的参与者(或不是参与者)，也是电子密度的源/汇。这一领域进行更多量化实验的时机似乎已经成熟。
In this Featured Article, I reflect on over 40 years of guided ion beam tandem mass spectrometry (GIBMS) studies involving atomic metal cations and their clusters throughout the periodic table. Studies that have considered the role of spin conservation (or lack thereof) are a primary focus with a quantitative assessment of the effects examined. A need for state-specific studies of heavier elements is noted, as is a more quantitative assessment of spin–orbit interactions in reactivity. Because GIBMS experiments explicitly evaluate the kinetic energy dependence of reactions over a wide range, several interesting and unusual observations are highlighted. More detailed studies of such unusual reaction events would be welcome. Activation of C–H bonds and ensuing C–C coupling events are reviewed, with future work encouraged. Finally, studies of lanthanides and actinides are examined with an eye on understanding the role of f orbitals in the chemistry, both as participants (or not) in the bonding and as sources/sinks of electron density. This area seems to be ripe for more quantitative experiments.