催化C-H水氧化机制研究揭示了催化剂停止的意想不到的途径
James B C Mack1, Katherine L Walker1, Sophia G Robinson2
1Department of Chemistry , Stanford University , 337 Campus Drive , Stanford , California 94305 , United States.
Journal of the American Chemical Society
|January 3, 2019
概括
鲁复合物催化C-H化,但性能因配体而异. 连接物解离和氧化为N-氧化物显著降低了催化剂的效率,并导致失活.
科学领域:
- 有机金属化学
- 催化剂
- 有机合成
背景情况:
- 复合物与2,2'-双 (bpy) 连接物是C-H化中的有效预催化剂.
- 在4,4'-di-tert-butyl-2,2'-bipyridine (dtbpy) 和未被替代的bpy配体之间存在显著的性能差异.
研究的目的:
- 调查Ru催化C-H化中的性能差异的机制起源.
- 了解催化剂分解路径,并确定改善催化剂设计的策略.
主要方法:
- 结合体结构与活性关系研究.
- 电化学和运动分析.
- 压缩样品输液高分辨率质谱 (PSI-MS).
主要成果:
- 确定了多种活性氧化剂和三种不同的催化剂分解途径.
- 催化剂效率 (周转率) 与连接物解离率相反相关.
- 分离的bpy配体可以被氧化为N-氧化物,它们作为催化剂毒素,形成不活跃的复合物.
结论:
- 连接剂替代剂对C-H化中的催化剂稳定性和效率具有重要影响.
- PSI-MS是阐明复杂的催化机制的强大工具.
- 了解失活路径可以开发下一代高性能Ru催化剂,用于C-H化.
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