螺旋式双核3d金属复合物与二 (双) [S,N]配体:合成,结构和计算研究
Jamie Allen1, Jörg Saßmannshausen2, Kuldip Singh1
1School of Chemistry, University of Leicester, University Road, Leicester, LE1 7RH, UK. sandy.kilpatrick@leicester.ac.uk.
Dalton transactions (Cambridge, England : 2003)
|October 15, 2024
概括
合成了新的双核金属复合体,具有独特的双链螺旋体结构. 这些复合物表现出强大的金属硫键和可访问的氧化还原特性,在协调化学中具有潜力.
科学领域:
- 协调化学 协调化学
- 超分子化学 超分子化学
- 材料科学 材料科学 材料科学
背景情况:
- 开发用于金属复合体合成的新型配体.
- 探讨金属-合金粘合和结构动图的研究.
- 研究过渡金属复合物的磁性和电子性质.
研究的目的:
- 合成和表征新型二蛋白 bis ((β-thioketoimine) 连接物及其金属复合物.
- 研究双核和单金属复合物的结构,电子和磁性特性.
- 使用计算方法阐明金属-硫和金属-结合的性质.
主要方法:
- 使用Lawesson的试剂合成一个bis ((β-thioketoimine) 连接物前体 (H22).
- 协调化学涉及化和与金属化物 (Fe,Co,Zn) 的反应.
- 通过X射线衍射进行结构性表征,通过DFT进行电子/磁性特性,进行磁性研究和循环电压测量.
主要成果:
- 形成具有双链螺旋体结构和四面体金属中心的同质双核复合体[M2(μ-2) 2].
- 观察到显著的跨链面对面 π 堆叠导致状扭曲 ~ 70°.
- DFT计算表明M-S债券比M-N债券更强,更共价;Fe (II) 和Co (II) 复合体表现出具有可访问的氧化还原活性的高旋转四面体中心.
结论:
- 成功合成了新的双核和单金属β-thioketoiminate复合体.
- 双核复合体采用独特的双链螺旋体结构,通过π堆叠稳定.
- 更强的MS结合和可访问的氧化还原特性突显了这些复合体在协调化学和材料科学中的潜力.
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