Eralie Dylan M T, Ducilon John, Gorden Anne E V
Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas 79401, United States.
Inorg Chem. 2025 Jan 20;64(2):767-784. doi: 10.1021/acs.inorgchem.4c02173. Epub 2024 Aug 27.
While uranium is the most extensively studied actinide in terms of chemical properties, there remains much to be explored about its fundamental chemistry. Organometallic and organoactinide chemistry first emerged in the 1950s with research that found inspiration from transition-metal chemistry with the synthesis and characterization of uranocene, expanding new opportunities for organoactinide chemistry. Since then, a significant amount of research has pursued many avenues characterizing the fundamental nature of the f orbitals and their modes of bonding as well as their potential in catalysis. Uranium(III/IV) arene complexes dominate much of uranium organometallic chemistry, with bonding interactions stabilized by δ-back-bonding. Recent additions to this area of chemistry include the first U and new additions of U organouranium compounds. Uranium-transition metal complexes are still rare and maintain U oxidation states, with variable bond lengths determining the transition-metal oxidation state. Resultant reactivities are discussed as synthetic complexes, and unique bonding and coordination motifs are highlighted. This Viewpoint will focus on significant developments in uranium chemistry from the last 15 years while considering key areas for future research.
虽然就化学性质而言,铀是研究最为广泛的锕系元素,但关于其基础化学仍有许多有待探索之处。有机金属化学和有机锕系元素化学最早出现在20世纪50年代,当时的研究从过渡金属化学中获得灵感,合成并表征了二茂铀,为有机锕系元素化学拓展了新机遇。从那时起,大量研究探索了许多途径,以表征f轨道的基本性质及其成键模式以及它们在催化方面的潜力。铀(III/IV)芳烃配合物在许多铀有机金属化学中占主导地位,其键合相互作用通过δ-反馈键得到稳定。该化学领域的最新进展包括首例铀有机铀化合物以及新的此类化合物。铀-过渡金属配合物仍然很少见,且保持铀的氧化态,可变的键长决定了过渡金属的氧化态。作为合成配合物讨论了由此产生的反应性,并突出了独特的键合和配位模式。本观点将聚焦过去15年铀化学的重大进展,同时考虑未来研究的关键领域。