合成和比较具有η-6-arene相互作用的异构结构f块金属复合物 (Ce,U,Np,Pu)
Jesse Murillo1,2, Conrad A P Goodwin2, Lauren Stevens2,3
1Department of Chemistry and Biochemistry, University of Texas at El Paso El Paso Texas 79968 USA asfortier@utep.edu.
Chemical science
|July 14, 2023
概括
这项研究探讨了新的f元素复合体,揭示了独特的金属相互作用和第一个6结构. 复合体表现出最短的金属-碳键,挑战了离子半径预测.
科学领域:
- 有机金属化学 有机金属化学
- 动因化物化学 动因化物化学
- 协调化学 协调化学
背景情况:
- 甲基 (甲基) 连接物为f元素提供独特的协调环境.
- 了解金属-烯相互作用对于f元素化学至关重要.
- 早期的活性化物 (U,Np,Pu) 和 (Ce) 具有不同的电子和硬质性质.
研究的目的:
- 用一个terphenyl bis ((anilide) 配体合成和表征新的f元素复合物.
- 研究这些M-η6-arene复合物的结构和结合特性.
- 为了比较早期的活性化物和之间的金属相互作用.
主要方法:
- [{K(DME) 2}2LAr]与MCl3 (M = Ce, U, Np) 和MI3 (M = Ce, U, Np, Pu) 盐的反应.
- 中性和阳离子f元素复合物的隔离和结构特征.
- 分析金属结合度指标,并与离子半径预测进行比较.
主要成果:
- 中性LArM(Cl) ((THF) 和LArM(I) ((THF) 复合物的合成 (M = Ce, U, Np, Pu).
- 对Ce和U而言,形成离子复合体[K(DME) 2][LAr) Np(Cl) 2和聚合物结构 ([LArM(Cl) 2(μ-K(X) 2) ]∞.
- 在所有复合体中观察n6-arene相互作用,包括第一个结构特征的Pun6-arene部分.
- 复合体表现出最短的M-C中心点距离,偏离离子半径趋势.
结论:
- 这项研究提供了对早期的乙化物和 η6-烯复合物的系统调查.
- 金属-烯键度指标并不严格遵循离子半径预测的趋势.
- 这些发现为f元素有机金属化合物的结合和结构多样性提供了新的见解.
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