三和四复合物及其在催化两极化转移中的作用,从平转移到pyruvate
Ben J Tickner1, Simon B Duckett2
1Centre for Hyperpolarisation in Magnetic Resonance, University of York Heslington YO10 5NY UK.
新型的化复合物通过依赖溶剂的反应形成. 这些化合物,包括具有独特连接体排列的四化物,是pyruvate超极化中的副产品,需要最小化以提高效率.
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.
- 频谱学是一种光谱学.
背景情况:
- 复合物在催化和超极化技术中至关重要.
- 了解金属化物复合体中的联结体效应是控制反应性的关键.
- 硫氧化配体可以诱导金属复合物的显著结构和电子变化.
研究的目的:
- 详细说明非同寻常的四化和三化复合物的形成.
- 为了研究前体与硫氧化物和的溶剂依赖反应性.
- 描述这些新型化物种的结构和反应途径.
主要方法:
- 使用[IrCl (COD) (IMes) ],硫氧化物,基和H2合成四和三复合物.
- 使用核磁共振 (NMR) 光谱学进行表征.
- 探测反应通路使用超极化 (PHPH) 的方法.
主要成果:
- 形成[Ir(H) 4(IMes) 氧化物]Na和[Ir(H) 3(IMes) 氧化物) 2复合体.
- 甲基二硫氧化物导致四化物与相应的化物和转链体.
- 由于对称性破裂,甲基硫氧化物产生了一个cis同位素四化物与四个不同的化物连接体.
- 这些复合物被确定为SABRE催化型酸盐超极化中的低度副产品.
结论:
- 溶剂和硫氧化物结构决定了复合物的异构结果和化物对称性.
- 这些化是SABRE超极化过程中以前未知的副产品.
- 降低这些副产品的度对于高极化应用中高效的极化转移至关重要.
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