Berkelium-carbon bonding in a tetravalent berkelocene

• 成果类型: Article
• 署名作者: Russo, Dominic R.; Gaiser, Alyssa N.; Price, Amy N.; Sergentu, Dumitru-Claudiu; Wacker, Jennifer N.; Katzer, Nicholas; Peterson, Appie A.; Branson, Jacob A.; Yu, Xiaojuan; Kelly, Sheridon N.; Ouellette, Erik T.; Arnold, John; Long, Jeffrey R.; Lukens Jr, Wayne W.; Teat, Simon J.; Abergel, Rebecca J.; Arnold, Polly L.; Autschbach, Jochen; Minasian, Stefan G.
• 署名单位: United States Department of Energy (DOE); Lawrence Berkeley National Laboratory; University of California System; University of California Berkeley; Alexandru Ioan Cuza University; Alexandru Ioan Cuza University; State University of New York (SUNY) System; University at Buffalo, SUNY; University of California System; University of California Berkeley; University of California System; University of California Berkeley; United States Department of Energy (DOE); Lawrence Berkeley National Laboratory; University of California System; University of California Berkeley
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-10340
• DOI: 10.1126/science.adr3346
• 发表日期: 2025-02-28
• 页码: 974-978
• 关键词: generalized-gradient-approximation; segmented contraction scheme; electronic-structure; molecular-structure; cyclooctatetraene dianion; oxidation-state; basis-sets; complexes; covalency; crystal

摘要

Interest in actinide-carbon bonds has persisted since actinide organometallics were first investigated for applications in isotope separation during the Manhattan Project. Transplutonium organometallics are rarely isolated and structurally characterized, likely owing to limited isotope inventories, a scarcity of suitable laboratory infrastructure, and intrinsic difficulties with the anaerobic conditions required. Herein, we report the discovery of an organometallic berkelocene complex prepared from 0.3 milligrams of berkelium-249. Single-crystal x-ray diffraction shows a tetravalent berkelium ion between two substituted cyclooctatetraene ligands, resulting in the formation of berkelium-carbon bonds. The coordination in berkelocene resembles that of uranocene, and calculations show that the berkelium 5f orbitals engage in covalent overlap with the delta-symmetry orbitals of the cyclooctatetraenide ligand pi system. Charge transfer from the ligands is diminished relative to uranocene and other actinocenes, which maximizes contributions from the stable, half-filled 5f7 configuration of tetravalent berkelium.