EaStCHEM School of Chemistry, University of Edinburgh, The King's Buildings, Edinburgh EH9 3FJ, UK.
European Commission, Joint Research Centre (JRC), Institute for Transuranium Elements (ITU), Postfach 2340, D-76125 Karlsruhe, Germany.
Nat Chem. 2016 Aug;8(8):797-802. doi: 10.1038/nchem.2520. Epub 2016 May 23.
Studies of transuranic organometallic complexes provide a particularly valuable insight into covalent contributions to the metal-ligand bonding, in which the subtle differences between the transuranium actinide ions and their lighter lanthanide counterparts are of fundamental importance for the effective remediation of nuclear waste. Unlike the organometallic chemistry of uranium, which has focused strongly on U(III) and has seen some spectacular advances, that of the transuranics is significantly technically more challenging and has remained dormant. In the case of neptunium, it is limited mainly to Np(IV). Here we report the synthesis of three new Np(III) organometallic compounds and the characterization of their molecular and electronic structures. These studies suggest that Np(III) complexes could act as single-molecule magnets, and that the lower oxidation state of Np(II) is chemically accessible. In comparison with lanthanide analogues, significant d- and f-electron contributions to key Np(III) orbitals are observed, which shows that fundamental neptunium organometallic chemistry can provide new insights into the behaviour of f-elements.
对超铀金属有机配合物的研究为金属-配体键合中的共价贡献提供了特别有价值的见解，其中，超铀锕系离子与其较轻的镧系元素对应物之间的细微差异对于有效处理核废料至关重要。与强烈关注 U(III)并取得了一些引人瞩目的进展的铀金属有机化学不同，超铀金属有机化学在技术上具有更大的挑战性，并且一直处于休眠状态。就镎而言，它主要限于 Np(IV)。在这里，我们报告了三种新的 Np(III)金属有机化合物的合成及其分子和电子结构的表征。这些研究表明，Np(III)配合物可以作为单分子磁体，并且 Np(II)的较低氧化态在化学上是可及的。与镧系元素类似物相比，观察到关键 Np(III)轨道中存在显著的 d 和 f 电子贡献，这表明基础的镎金属有机化学可以为 f 元素的行为提供新的见解。
