作为兰化集群的构建块的真:一个铜集群被一个兰化集群封装
Nicholas Arleth1, Sebastian Bestgen, Michael T Gamer
1Institut für Anorganische Chemie, Karlsruher Institut für Technologie (KIT) , Engesserstrasse 15, Geb. 30.45, 76131 Karlsruhe, Germany.
Journal of the American Chemical Society
|September 24, 2014
概括
兰化金属与硫化反应,形成新的开放和封闭子复合物. 一个独特的萨马-铜集群封装了一个铜四面体,标志着f元素封装化学的首次出现.
科学领域:
- 有机金属化学 有机金属化学
- 协调化学 协调化学
- 无机化学 无机化学
- 材料科学 材料科学 材料科学
背景情况:
- 兰化金属是协调化学中的多功能前体.
- 硫化 (As4S4,As4S3) 是具有丰富反应性的无机化合物.
- 合成涉及f元素的新化合物仍然是一个重大挑战.
研究的目的:
- 为了探索双价兰化金属与硫化物之间的反应性.
- 为了合成和表征新的开放和封闭的子复合体.
- 研究涉及f元素和过渡金属的内分层集群的形成.
主要方法:
- 兰坦化金属 ([Cp*2Ln(thf) 2 ,[Cp′′′2Sm]) 与真 (As4S4) 和二态 (As4S3) 的反应.
- 通过与[CuMes]反应合成一个-硫-铜集群.
- 使用光谱和晶体学技术对产生的复合体进行表征.
主要成果:
- 形成开放的四金属 (Cp*2Sm) 和三金属 (Cp*Yb) 复合体.
- 关闭的11个顶点的子集群的合成 [(Cp′′′Sm) 3 ((AsS3) 2) 和 [(Cp*Yb) 3 ((AsS3) 2].
- 发现了第一个f元素封装过渡金属素化集群,[(Cp′′′Sm(thf)) 4Cu4S6],在一个硫化集群中显示一个Cu4四面体.
结论:
- 双重兰化金属与硫化物表现出多样化的反应性,导致新的子结构.
- 该研究引入了前所未有的Cp*AsS2(2-) 离子和协调化学中的As2S4(4-) 离子.
- 一个Cu4S6集群的成功封装由化金属衍生物打开了集群化学和材料科学的新途径.
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