佐治亚理工学院Henry S. La Pierre研究组取得一项新突破。他们开发出正态+5氧化态的镨。相关论文于2025年4月7日发表在《自然—化学》杂志上。

本文报道了一种正态+5氧化态镨配合物[Pr⁵⁺(NP^tBu₃)₄][X^-］(^tBu = 叔丁基，X^-=四（五氟苯基）硼酸盐或六氟磷酸盐)。单晶x射线衍射、溶液态光谱、溶液磁强学、密度泛函理论和基于多参考波函数的方法表明了一个高度多构型的单重态基态。一个反向配体场驱动这种独特的电子结构，它建立了理解跨元素周期表的高价金属配合物的键合的关键环节。

据悉，镨在+5氧化态是长期寻求镧系，早期转变和锕系金属氧化还原化学之间的联系。独特的镧系元素中，分子五价镨物种的证据已在气相和惰性气体基质分离条件下观察到。

附：英文原文

Title: Praseodymium in the formal +5 oxidation state

Author: Boggiano, Andrew C., Studvick, Chad M., Roy Chowdhury, Sabyasachi, Niklas, Julie E., Tateyama, Haruko, Wu, Hongwei, Leisen, Johannes E., Kleemiss, Florian, Vlaisavljevich, Bess, Popov, Ivan A., La Pierre, Henry S.

Issue&Volume: 2025-04-07

Abstract: Praseodymium in the +5 oxidation state is a long-sought connection between lanthanide, early-transition and actinide metal redox chemistries. Unique among the lanthanide series, evidence for molecular pentavalent praseodymium species has been observed in the gas phase and noble gas matrix isolation conditions. Here we report the low-temperature synthesis and characterization of a molecular praseodymium complex in the formal +5 oxidation state, [Pr5+(NPtBu3)4][X] (where tBu=tert-butyl and X=tetrakis(pentafluorophenyl)borate or hexafluorophosphate). Single-crystal X-ray diffraction, solution-state spectroscopic, solution magnetometric, density functional theory and multireference wavefunction-based methods indicate a highly multiconfigurational singlet ground state. An inverted ligand field drives this unique electronic structure, which establishes a critical link in understanding the bonding of high-valent metal complexes across the periodic table.

DOI: 10.1038/s41557-025-01797-w

Source: https://www.nature.com/articles/s41557-025-01797-w