Hop-Skip-Jump: Monovalent Metals on the Surface of the Phenalenyl Radical,Organometallics

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Hop-Skip-Jump: Monovalent Metals on the Surface of the Phenalenyl Radical
Organometallics ( IF 2.5 ) Pub Date : 2019-12-24 , DOI: 10.1021/acs.organomet.9b00564
Supreeth Prasad ₁ , Noah Walker ₁ , Michael Henry ₁ , Kelling J. Donald ₁

Affiliation

The phenalenyl radical (P) and its relatively stable cation and anion are of interest for applications in areas spanning magnetic materials and ligand development for reaction catalysis. We report on a broad investigation of the bonding, thermochemistry, and kinetics of PM complexes where M is a group 1 or 11 metal atom. The PM species that are considered in this work afford a simplified picture of the behavior of metal adatoms on hydrogen terminated graphene fragments, and, more crucially, we expand a still nascent understanding of the organometallic chemistry of P. The exceptional fluxionality of group 1 metals on the phenalenyl surface is predicted, the associated energy barriers are quantified, and the major role of relativistic effects in restricting the fluxionality of Au on the surface is demonstrated. Although relativistic effects swell the barriers to isomerization, we find that orbital size and energies, even in the absence of relativistic effects, dictate different path preferences for the motion of Au on the surface of the radical compared to Cu and Ag.

中文翻译：

Hop-Skip-Jump：苯甲醛基自由基表面上的一价金属

苯乙炔基（P）及其相对稳定的阳离子和阴离子对于跨越磁性材料和用于反应催化的配体发展领域具有重要意义。我们报告了键合，热化学和动力学的动力学复杂的P M配合物，其中M是1或11组金属原子。在这项工作中考虑的P M物种提供了氢吸附石墨烯碎片上金属吸附原子行为的简化图，更重要的是，我们扩展了对P有机金属化学的了解。。预测了苯甲烯基表面上第1组金属的异常通量，量化了相关的能垒，并证明了相对论效应在限制Au在表面上的通量的主要作用。尽管相对论效应扩大了异构化的障碍，但我们发现，即使没有相对论效应，轨道尺寸和能量也决定了与铜和银相比，Au在自由基表面上的运动具有不同的路径偏好。

更新日期：2019-12-25

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