EaStCHEM School of Chemistry, University of Edinburgh , The King's Buildings, Edinburgh, EH9 3FJ, U.K.
European Commission, DG Joint Research Centre, Directorate G-Nuclear Safety and Security, Advanced Nuclear Knowledge-G.I.5, Postfach 2340, D-76125, Karlsruhe, Germany.
Chem Rev. 2017 Sep 13;117(17):11460-11475. doi: 10.1021/acs.chemrev.7b00192. Epub 2017 Aug 30.
Fifty years have passed since the foundation of organometallic neptunium chemistry, and yet only a handful of complexes have been reported, and even fewer have been fully characterized. Yet, increasingly, combined synthetic/spectroscopic/computational studies are demonstrating how covalently bonding, soft, carbocyclic organometallic ligands provide an excellent platform for advancing the fundamental understanding of the differences in orbital contributions and covalency in f-block metal-ligand bonding. Understanding the subtleties is the key to the safe handling and separations of the highly radioactive nuclei. This review describes the complexes that have been synthesized to date and presents a critical assessment of the successes and difficulties in their analysis and the bonding information they have provided. Because of increasing recent efforts to start new Np-capable air-sensitive inorganic chemistry laboratories, the importance of radioactivity, the basics of Np decay and its ramifications (including the radiochemical synthesis of one organometallic compound), and the available anhydrous starting materials are also surveyed. The review also highlights a range of instances in which important differences in the chemical behavior between Np and its closest neighbors, uranium and plutonium, are found.
五十年来，金属有机镎化学已经奠基，但据报道，仅有少数配合物，而且更少得到了完全的表征。然而，越来越多的综合合成/光谱/计算研究正在展示如何通过共价键合、柔软、碳环有机金属配体，为推进对 f 区金属-配体键合中轨道贡献和共价性的差异的基本理解提供了极好的平台。理解细微差别是安全处理和分离高放射性核素的关键。本综述描述了迄今为止合成的配合物，并对它们的分析及其提供的键合信息的成功和困难进行了批判性评估。由于最近越来越多地努力启动新的能够处理镎的空气敏感无机化学实验室，放射性的重要性、镎衰变的基本原理及其影响（包括一种有机金属化合物的放射化学合成）以及可用的无水起始材料也进行了调查。该综述还强调了在镎与其最接近的邻居铀和钚的化学行为之间存在重要差异的一系列实例。
