金属/连接体质子陶托美化促进双核H2的减少性淘汰
Jonathan L Kuo1, Karen I Goldberg1
1Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States.
Journal of the American Chemical Society
|December 10, 2020
概括
这项研究合成了一种化复合物,表现出金属/联结体质子共聚性,可由外部联结体控制. 这种平衡促进了气的产生,并为质子响应催化剂设计提供了新的策略.
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.
- 协调化学 协调化学
背景情况:
- 金属复合体中的质子共聚对于催化活性至关重要.
- 控制金属-联体质子平衡是设计响应性催化剂的关键.
研究的目的:
- 合成和描述一个新的八面体Ir (III) - 化物复合体.
- 为了研究金属/联结体质子共聚性及其通过外源联结体的控制.
- 阐明从化复合物中产生H2的机制.
主要方法:
- 从一个Ir(I) 前体合成一个八面体的Ir(III) - 化物复合体 ([1-MH]+).
- 紫外线光谱学用于研究金属化物和带质子物种之间的平衡.
- 机理研究,以确定H2生成和Ir (II) 二次体形成的途径.
主要成果:
- 成功合成了Ir (III) - 化物复合物[HIr (κ3) -N (NH) -N (NN-)) -CO (tBuPy) ]+ ([1-MH]+).
- 观察[1-MH]+和正方形平面的Ir(I) 物种 ([2-LH]+) 之间的[tBuPy]依赖平衡.
- 证明[1-MH]+的2等值在温和条件下释放H2形成Ir(II) 模态 ([7]2+).
结论:
- 金属/联结体质子共聚性可以通过外源联结体度来控制.
- 这种分体化为配体解离提供了低能耗的途径,使H2产生.
- 这些发现引入了一种新的策略,用于设计基于受控复合的质子响应催化剂.
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