基于二氧化二胺的高价值碳二氧化二氧化二氧化碳基钉复合物的合成,特征和反应性
Aniruddha Sarkar1, Soumadip Das1, Prasenjit Mondal2
1Department of Chemical Sciences, Indian Institute of Science Education and Research (IISER) Kolkata, Mohanpur 741246, India.
Inorganic chemistry
|November 24, 2023
概括
本研究探讨了用于协同质子电子转移 (CPET) 反应的高价值化复合物与N-异环碳联体. 新的碳二化物Ni(III) - 化物复合物显示出与类的反应性,由其氧化还原潜力驱动.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
- 反应机制 反应机制
背景情况:
- 高价值的金属化物复合物被研究为协调的质子电子转移 (CPET) 反应.
- 化具复合物与化连接物已在CPET反应中表现出实用性.
- 在稳定高价值状态和促进CPET方面,N-异环碳化合物 (NHC) 连接体的作用尚未得到充分研究.
研究的目的:
- 为了合成和表征一种基于碳二胺的新型Ni (II) - 化物针复合物.
- 评估NHC连体对高价值Ni (III) 状态的稳定性的影响.
- 为了研究由此产生的Ni (III) - 化物复合物与的CPET活性.
主要方法:
- 使用NMR,质谱学,UV-vis和X射线晶体学合成和表征Ni(II) - 化物复合物.
- 氧化到Ni (III) - 化物模拟物使用酸 (CTAN).
- 通过紫外线,质谱学和EPR光谱学对Ni (III) 物种的特征.
- 使用密度函数理论 (DFT) 的计算研究.
- 动力学研究包括动力同位素效应 (KIE) 和线性自由能量关系.
主要成果:
- 一个基于碳二胺的单体化物合物合物合物合物复合物成功合成和特征化.
- 在高,不可逆转的电位 (0.87 V 与 Fc+/Fc) 发生氧化到Ni(III) 状态.
- DFT的计算显示了氧化后的Ni-carbene键的延长和Ni-F键的缩短.
- 化复合物与替代的反应,表现出CPET的特征.
- 动力学分析证实了反应的CPET性质,表明主要由复合物的氧化还原潜力驱动的异步机制.
结论:
- NHC配体可以稳定高价值化物种,尽管它们会诱导显著的结构扭曲.
- 合成的Ni (III) - 化物复合物能够调解CPET与的反应.
- 反应机制是异步的,并受到Ni(III) - 化物复合物的氧化还原特性的影响.
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