美国佐治亚理工学院Henry S. La Pierre研究团队研制了一种四面体的镎(V)配合物。这一研究成果于2024年5月6日发表在国际顶尖学术期刊《自然-化学》上。

该文报道了一个四面体分子镎(V)配合物([Np⁵⁺(NPC)₄][B(ArF₅)₄], 1-Np) (NPC=[NP^tBu(pyrr)₂]^-; tBu=C(CH₃)₃; pyrr=pyrrolidinyl(N(C₂H₄)₂); B(ArF₅)₄=tetrakis(2,3,4,5,6-pentaflutheirophenyl)borate). 对1-Np及其质子耦合电子转移(PCET)反应产物2-Np的单晶X射线衍射、溶液态光谱和密度泛函理论研究，证明了稳定该反应离子的独特键合，并建立了凝聚相超铀配合物中PCET的热化学和动力学参数。

这种配位的镎(V)配合物的分离揭示了超铀化学中一条基本的反应途径。

据介绍，镎是一种人造的锕系元素，与天然丰富的铀不同，它的配位化学并没有在所有可能的氧化态中被发展。高价镎通常需要至少一个金属配体多键的稳定，并且离开这个结构基序带来了可想而知的挑战。

附：英文原文

Title: A tetrahedral neptunium(V) complex

Author: Niklas, Julie E., Otte, Kaitlyn S., Studvick, Chad M., Roy Chowdhury, Sabyasachi, Vlaisavljevich, Bess, Bacsa, John, Kleemiss, Florian, Popov, Ivan A., La Pierre, Henry S.

Issue&Volume: 2024-05-06

Abstract: Neptunium is an actinide element sourced from anthropogenic production, and, unlike naturally abundant uranium, its coordination chemistry is not well developed in all accessible oxidation states. High-valent neptunium generally requires stabilization from at least one metal–ligand multiple bond, and departing from this structural motif poses a considerable challenge. Here we report a tetrahedral molecular neptunium(V) complex ([Np5+(NPC)4][B(ArF5)4], 1-Np) (NPC=[NPtBu(pyrr)2]; tBu=C(CH3)3; pyrr=pyrrolidinyl (N(C2H4)2); B(ArF5)4=tetrakis(2,3,4,5,6-pentafluourophenyl)borate). Single-crystal X-ray diffraction, solution-state spectroscopy and density functional theory studies of 1-Np and the product of its proton-coupled electron transfer (PCET) reaction, 2-Np, demonstrate the unique bonding that stabilizes this reactive ion and establishes the thermochemical and kinetic parameters of PCET in a condensed-phase transuranic complex. The isolation of this four-coordinate, neptunium(V) complex reveals a fundamental reaction pathway in transuranic chemistry.

DOI: 10.1038/s41557-024-01529-6

Source: https://www.nature.com/articles/s41557-024-01529-6