与NHC结合的二氧化 () (-1) 复合物:合成,表征和它们的二氧化功能化反应
Yafei Gao1, Guangyu Li1, Liang Deng1
1State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences , 345 Lingling Road, Shanghai 200032, P. R. China.
本研究使用N-异环碳联体合成了新型-二复合物,证明了它们在固定反应和产生和复合物的有效性. 这些发现突显了低价值物种在催化转化中的潜力.
科学领域:
- 有机金属化学
- 催化剂
- 固定气
背景情况:
- 晚期过渡金属复合物对于 (N2) 固定至关重要,但由于N2复合物的可变性和难以功能化,它们的反应性,尤其是铁之外的反应性,仍然不太清楚.
- N-异环碳素 (NHC) 连接物具有独特的固体和电子特性,可以稳定反应性金属中心.
研究的目的:
- 使用特定的NHC配体 (ICy) 合成和表征新的-二复合物.
- 研究这些复合体在N2功能化反应中的反应性,包括质子化和化.
- 评估这些复合物的催化活性,以减少N2的化.
主要方法:
- 通过在N2下逐步降低前体,合成(0) 和(-1) N2复合体,[(ICy)3Co(N2) 和[(ICy)2Co(N2)2Mn.
- 使用X射线衍射,光谱 (IR) 和计算方法进行复合物的表征.
- 固体测量反应包括三酸的质子化和化的反应.
- 在N2的还原性化中进行催化试验.
主要成果:
- 通过 ICy 配体稳定 ((0) -N2和 ((-1) -bis() 复合物的成功合成.
- 通过N-N键距离和红外拉伸频率证明了在 (-1) 复合体中的N2激活.
- 通过质子化形成素 (N2H4),并从N2功能化中形成第一个过渡金属烯复合体.
- NHC-cobalt复合物表现出N2的有效催化,实现与其他3d金属催化剂相比或超过的周转率.
结论:
- 这项研究确定了NHC连接体在稳定反应性N2物种中的有用性,从而实现了前所未有的N2功能化.
- 低价值,低坐标的9组金属复合物对N2固定和催化应用具有显著的前景.
- 这些发现为开发高效的转化催化剂开辟了新的途径.
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