氧原子从非血N4-协调Fe ((IV) O转移到烯之间的竞争和水加速对比
Yanrong Zhang1, Marika Di Berto Mancini1, Iris Meindertsma1
1Molecular Inorganic Chemistry, Stratingh Institute for Chemistry, Faculty of Science and Engineering, University of Groningen, Nijenborgh 3, 9747 AG Groningen, The Netherlands.
Inorganic chemistry
|January 12, 2026
概括
非血红素铁 (IV) 氧化物复合物是催化过程中的关键中间体. 这项研究在室温下产生了稳定的铁氧化物复合物,揭示了其反应性和水在催化氧化过程中阻碍其观察的作用.
科学领域:
- 无机化学 无机化学 有机化学
- 催化剂是一种催化剂.
- 氧化反应 氧化反应
背景情况:
- 非血红素铁 (IV) 氧化物复合物是催化有机氧化过程中的中介物.
- 这些中间体通常不会在室温下与H2O2一起观察到,这是由于快速反应或分解.
- [{MeN3Py) Fe{II) }{CH3CN) ]2+ (1) 是一种具有 cis-溶剂协调性的代表性Fe{II) 催化剂.
研究的目的:
- 在室温下生成和表征非血红素铁 (IV) 氧化物复合物.
- 为了研究铁(IV) 氧化物复合物在氧原子转移反应中的反应性.
- 阐明影响铁(IV) 氧化物中间体在催化循环中的稳定性和观察因素.
主要方法:
- 在没有水和H2O2.2的情况下,在现场氧化非海姆Fe (II) 复合物[MeN3Py) Fe (II) (CH3CN) ]2+使用酸 (PhPAA).
- 生成的Fe(IV) O复合体[(MeN3Py) ((CH3CN) Fe(IV) O]2+ (4) 的表征.
- 研究复合物4与烯的氧原子转移 (OAT) 反应,并分析竞争的路径,如比例化.
主要成果:
- 在室温中,Fe(IV) O复合物4在适度产量下使用无水/无H2O2的过氧酸 (PhPAA) 生成.
- 观察到氧原子从4转移到烯,再生Fe (II) 催化剂1.
- 与非活性Fe (III) 物种的比例与OAT竞争,而这种途径是由水加速的.
- 水和酸促进带交换以产生Fe(IV) O,但也加速有害的比分.
结论:
- 在特定条件下 (无水/无H2O2) 可以在室温下生成和观察稳定的非血红铁 (IV) 氧化物复合物.
- 水在加速Fe(IV) O中间体的分解中起着至关重要的作用,解释了它在基于H2O2的氧化过程中缺失的原因.
- 了解这些相互竞争的途径对于设计高效的氧化反应非血红素铁催化剂至关重要.
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