一个运行不和的-复合物,C-H激活晶体固态中的甲和乙
Matthew R Gyton1, M Arif Sajjad2, Daniel J Storm2
1Department of Chemistry, University of York, Heslington, York YO10 5DD, U.K.
这项研究表明,一种特定的复合体经历了甲和乙的单晶到单晶C-H激活. 这种固态反应途径与其溶液行为不同,为功能化提供了新的途径.
科学领域:
- 有机金属化学
- 固态化学
- 催化剂
背景情况:
- 复合物[Ir(tBu-PONOP) MeH][BArF4] (1[BArF4]) 是已知的C-H激活的前体.
- 溶液研究显示1[BArF4]与甲损失的分解,与所需的反应性形成对比.
- 了解固态反应性对于开发新的催化过程至关重要.
研究的目的:
- 研究复合物1[BArF4]对甲和乙的固态C-H激活.
- 阐明涉及C-H激活的单晶转化机制.
- 将固态反应与已知的溶液相行为进行比较.
主要方法:
- 单晶X射线衍射和中子衍射研究.
- 固态核磁共振 (SSNMR) 光谱,包括同位素标记.
- 密度函数理论 (DFT) 的计算.
- 在各种条件下的反应 (真空,N2,CO,乙大气).
主要成果:
- 1[BArF4]在80°C时经历可逆单晶到单晶 (SC-SC) 的甲激活,形成循环金属化[Ir(cyclo-tBu-PONOP') H][BArF4] (2[BArF4]).
- 复合物2[BArF4]作为一种活性的不和来源,促进了进一步的C-H激活和脱.
- 与N2和CO的反应也通过SC-SC转换进行,DFT计算提供了机械洞察力.
结论:
- 固态环境允许通过SC-SC转换对甲和乙进行强有力的和可逆的C-H激活,这与溶液的行为不同.
- 环金属化中间体2[BArF4]是各种反应的通用前体,包括脱和小分子协调.
- 这项工作突显了固态反应对受控功能化和催化作用的潜力.
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