一个线性两个坐标的Cr (II) 复合体:合成,表征和反应性
Kai-Chin Hsiao1, Po-Chun Yang1, Chia-Te Fang1
1Department of Chemistry, National Cheng Kung University, No. 1 University Road, 701401, Tainan, Taiwan.
Chemistry, an Asian journal
|December 7, 2023
概括
这项研究报告了线性双坐标(II) 胺基复合物的合成. 研究了氧化反应,产生各种 (III), (IV) 和 (VI) 复合物,并进行了DFT计算.
科学领域:
- 有机金属化学 有机金属化学
- 无机化学 无机化学 有机化学
- 协调化学 协调化学
背景情况:
- 线性,双坐标的金属复合体是罕见的,并且由于其独特的电子特性而引起了人们的兴趣.
- 胺化合物复合物是各种化学转换的宝贵前体.
- 了解低坐标复合物的反应性对于开发新的催化系统至关重要.
研究的目的:
- 为了合成和表征一种新的线性双坐标(II) 胺基复合物.
- 为了研究这个复合体与各种氧化剂和基质的氧化反应.
- 用计算方法阐明由此产生的复合体的电子结构.
主要方法:
- 通过CrCl2和LiN(tBu) Dipp的反应合成(II) 胺基复合物.
- 单晶X射线衍光测量 (SC-XRD) 用于结构的确定.
- 与AgOTf,[FeCp2][BArF4],有机亚化物,Me3NO和碳二化物进行氧化反应.
- 密度函数理论 (DFT) 计算用于电子结构分析.
主要成果:
- 成功合成和表征线性双坐标的Cr{(II) 胺基复合体,Cr{N(tBu) Dipp}2,具有短Cr-N键.
- 在与AgOTf和[FeCp2][BArF4]氧化后形成三角平面和曲的Cr(III) 复合体.
- 合成三坐标的Cr(IV) imido复合物与有机亚化物,以及一个Cr(VI) 二氧化复合物与Me3NO.
- 在Cr-N键中插入碳二胺基,产生三坐标的Cr (II) 复合体.
- DFT计算提供了对合成复合物的电子结构的见解.
结论:
- 合成的线性双坐标Cr(II) 胺基复合物是获得更高氧化状态复合物的多功能前体.
- 反应性概况证明了胺配体能够稳定的各种氧化状态的能力.
- 这项工作扩大了低坐标化学的范围,并为未来的催化应用提供了基础.
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