在晶体中,晶格适应性是由化组7复合体的固体-气体反应引发的
Joe C Goodall1, M Arif Sajjad2, Emily A Thompson1
1Department of Chemistry, University of York, York, YO10 5DD, UK.
概括
7组金属复合体表现出与一氧化碳 (CO) 的固体气体反应性. 复合物经历THF替代,而复合物显示CO添加,具有明显的对抗离子反应.
科学领域:
- 有机金属化学 有机金属化学
- 固态化学 固态化学
- 协调化学 协调化学
背景情况:
- 已知催化剂是7组金属复合物与氨酸联体.
- 固体-气体反应为化学转化提供了独特的途径.
- 对抗离子在固态反应性中的作用尚未完全理解.
研究的目的:
- 为了研究7组金属复合物的与一氧化碳的晶体反应性.
- 为了比较和复合体之间的反应性和结构变化.
- 了解对抗离子对固态反应的影响.
主要方法:
- 第7组金属复合物的合成 [M(κ3-2,6-(R2PO) 2C5H3N) ((CO) 2L][BArF4].
- 固体复合物的暴露于一氧化碳气体.
- 用X射线结晶学分析反应前后的结构变化.
主要成果:
- 复合物 (M=Mn,R=iPr,L=THF) 在暴露于CO时经历了选择性的THF替代.
- 复合体 (M=Re,R=tBu,L=空位) 经历了CO的添加.
- 对于Mn,观察到[BArF4]离子中的显著局部适应性变化,与Re的较小,远程变化形成鲜明对比.
结论:
- 7组金属复合物可以表现出可调节的固体-气体反应性.
- 金属和连接体环境的性质会影响反应路径 (替代与添加).
- 反离子动力学在固态反应中起着至关重要的作用,在不同的金属中心观察到不同的反应.
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