水母类型的二核哈夫酸复合物:合成和反应性
Xin-Cheng Lin1, Yun-Shu Cui1, Si-Jun Xie1
1Department of Chemistry, Fudan University, Shanghai, 200433, P. R. China.
Chemistry, an Asian journal
|September 13, 2023
概括
新的双核哈夫复合物用一种独特的pyrazolate桥接联体被合成. 减少一个哈夫胺复合物产生了一个四核哈夫胺复合物,显示出独特的反应性.
科学领域:
- 有机金属化学 有机金属化学
- 协调化学 协调化学
- 无机合成 无机合成
背景情况:
- 在科学文献中,被连接物桥接的二核和多核 hafnium 复合体很少被报道.
- 新子的合成对于进入新的协调环境和金属复合体中的反应性至关重要.
研究的目的:
- 设计和合成一种能够支持双核 hafnium 复合物的新型 pyrazolate-bridged 连接体.
- 探索新型双核哈夫氧化物复合物的合成和结构特征.
- 研究这些复合物的反应性,特别是在还原条件下,并阐明反应机制.
主要方法:
- 合成和表征一种新型的3,5-非替代的酸盐桥接联体 (LH5) 与[N2N]2-类别的化侧臂.
- 使用X射线晶体学准备和结构阐明双核哈夫酸复合物.
- 通过减少实验和DFT计算来研究复杂的反应性,以了解反应途径.
主要成果:
- 成功合成了一种支持双核 hafnium 复合物的新型 pyrazolate-bridged 连接体.
- 两种双核哈酸复合物的表征,[LHf2(μ-1,1-N3) 2(N3) 2) [Na(THF) 4) 3) 和[LHf2(μ-1,1-N3) 2(N3) 2) [Na(2,2,2-Cryptofix) ] (4),具有独特的桥梁和终端亚酸连接体.
- 从复合体3的减少中形成一个四核哈夫像素复合体 ([L1Hf2(μ1-NH) (((N3) {μ2-K}]2 5),表明了分子内C-H插入.
结论:
- 这种新型的pyrazolate桥接连体有效地支持二核 hafnium 复合物的形成.
- 双核 hafnium azide 复合物表现出有趣的结构特征和反应性.
- DFT的计算支持了通过HfIV-nitridyl中间体形成四核哈夫像素复合物的拟议机制.
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