在和酸复合体上对和酸协调的可逆结合
Marius Papendick1, Dietrich Gudat1
1Institut für Anorganische Chemie, University of Stuttgart, Pfaffenwaldring 55, 70550, Stuttgart, Germany.
Chemistry (Weinheim an der Bergstrasse, Germany)
|August 31, 2023
概括
N-arylated N-heterocyclic phosphenium manganese复合物的与H2的反应显示出不同的路径. 一个复合物经历H2的添加,而另一个是脱碳化物,导致不同的产品和受固体因素影响的反应性.
科学领域:
- 有机金属化学 有机金属化学
- 摄影化学的使用.
- 催化剂是一种催化剂.
背景情况:
- 在协调化学中,N-arylated N-heterocyclic phosphenium (NHP) 连接物具有独特的电子和硬质性质.
- 碳基复合物由于其反应性和潜在的催化应用而引起人们的兴趣.
研究的目的:
- 为了研究[{RNHP}Mn{CO}4]复合物与高压下H2的反应.
- 阐明影响这些复合物的反应性的机械路径和因素.
- 探索这些系统在光诱导化反应中的潜力.
主要方法:
- 核磁共振 (NMR) 光谱用于反应监测.
- 紫外线照射以启动光化学反应.
- 密度函数理论 (DFT) 计算以了解电子和硬质效应.
- 反应产品的分离和光谱表征.
主要成果:
- 两个[{RNHP}Mn{CO}4]复合体与H2 (约. 4 酒吧) 的时间.
- 复合物5a (R=Dipp) 通过在Mn=P键上添加H2产生了 (RNHP-H) MnH (CO) 4 (6a).
- 复合物5b (R=Mes) 经过脱碳化,形成二次物种[(RNHP) 2Mn2(CO) [7] (7b),该物种对H2.2无反应.
- DFT研究表明,固体拥堵会影响反应途径的分歧.
- 复合物5a/H2和6a初步显示了光诱导的乙烯化潜力.
结论:
- 反应结果取决于中间脱碳化物种的稳定性和反应性,受NHP配体的硬质因子的影响.
- 观察到的反应性差异凸显了NHP-复合物的可调性.
- 初步发现表明,在光诱导化中有潜在的应用,尽管机制需要进一步研究.
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