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用Ca,Sr,Yb和Sm减少的相似之处和差异:对四阳性的有力证据

Sandeep Kumar Thakur¹, Nil Roig^2,3, Roger Monreal-Corona^2,4

¹Inorganic and Organometallic Chemistry, Universität Erlangen-Nürnberg, Egerlandstrasse 1, 91058, Erlangen, Germany.

Angewandte Chemie (International ed. in English)

|April 13, 2024

概括

研究人员使用重的β-二甲胺酸 (BDI) 连接物合成了 (Yb) 和 (Sm) 的逆三明治复合物. 他们确定萨马复合物具有Sm(III) -(-4) -Sm(III) 结构,与相似的和复合物不同.

科学领域:

有机金属化学有机金属化学
兰化物化学兰化物化学
协调化学协调化学

背景情况:

反向三明治复合体的特点是金属原子与平面芳香联体协调.
在这种复合体中,协调联体的形式电荷经常受到争议,并影响金属氧化状态的赋值.
β-二甲基二胺酸 (BDI) 连接体为兰坦化物复合体提供固体质量和电子稳定.

研究的目的:

合成和描述由BDI配体稳定的 (Yb) 和 (Sm) 的逆三明治复合体.
研究这些复合体中的电子结构和结合,特别是协调的形式电荷.
为了比较Yb和Sm复合物的结构和电子特性与它们的土金属同类 (Ca和Sr).

主要方法:

合成 (BDI) Ln(η6,η6-C6H6) Ln(BDI) 复合体,其中Ln = Yb或Sm.
使用X射线晶体学进行结构性表征.
光谱分析包括NMR.
测量磁感应度的测量.
反应性研究.
计算调查 (例如,DFT).

主要成果:

成功制备了Yb和Sm与BDI配体的逆三明治复合体.
结构比较显示了Ca/Yb之间的相似性和Sr/Sm复合体之间的差异.
在Sm复合体中,较短的Sm-N和Sm-C6H6键距离强烈暗示了Sm(III) -(-4) -Sm(III) 赋值.
核磁共振,磁性,反应性和计算数据支持拟议的Sm(III) 氧化状态和四离子联体.

结论:

这项研究提供了强有力的证据,证明合成的逆三明治复合体中存在Sm{III}-{-4) -Sm{III}电子配置.
这与相似复合体中可能存在的Sm(II) 状态形成鲜明对比,突出显示了连接物环境和金属选择的影响.
这些发现有助于理解f元素有机金属化学中的结合和氧化状态的确定.

关键词:

芳香性是一种芳香性.烯是一种烯.减少减少减少萨马里亚姆 (Samarium) 是一个神器.这里是 Ytterbium 的位置.

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