高氧化物复合物的短暂形成和反应性
Sandeep K Padamati1, Davide Angelone1,2, Apparao Draksharapu1
1Molecular Inorganic Chemistry, Stratingh Institute for Chemistry, Faculty of Science and Engineering, University of Groningen , Nijenborgh 4, 9747AG, Groningen, The Netherlands.
Journal of the American Chemical Society
|June 6, 2017
概括
研究人员报告了一种在室温下形成的双核 (IV) 氧化物桥梁复合物. 在选择性氧化反应中,这种高价值的氧物种为控制低酸盐的反应性提供了新的可能性.
科学领域:
- 无机化学
- 有机金属化学
- 催化剂
背景情况:
- 高价金属氧物种是氧化催化过程中的关键中间体.
- 稳定和表征双核高价复合物存在重大挑战.
- 了解Ni ((IV) O物种的电子和结构性质是释放其催化潜力的关键.
研究的目的:
- 合成和描述一种新型的高反应性二核 (IV) 氧化物桥梁复合物.
- 研究Ni (IV) -O物种的结构和电子特性.
- 探索这个复合物与有机基质的选择性氧化反应.
主要方法:
- 通过与酸盐反应合成双核 (IV) 氧化物桥梁复合物.
- 使用紫外线吸收,共振拉曼,1H NMR,EPR和X射线吸收光谱的结构和电子表征.
- 使用密度函数理论 (DFT) 方法和ESI质谱的计算分析.
主要成果:
- 在室温下形成稳定的双核 (IV) 氧化物桥接复合物[L) 2Ni (IV) 2 (μ-O) 3+).
- 详细的结构和光谱证据证实了Ni (IV) -O连接和二核核.
- 证明与有机基质的反应性,表明有选择性氧化.
结论:
- 一个高价值的二核 (IV) 氧化物桥梁复合物的成功合成和表征.
- 这种Ni (IV) -O物种为研究基本反应性和开发新的催化氧化方法提供了平台.
- 开辟了选择性有机转化中控制的低反应的途径.
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