探测"旋转禁止"的氧原子转移: - 氨酸复合物的气相反应
Maria Elisa Crestoni1, Simonetta Fornarini, Francesco Lanucara
1Dipartimento di Studi di Chimica e Tecnologia delle Sostanze Biologicamente Attive, Università di Roma La Sapienza, P.le A. Moro 5, I-00185 Roma, Italy. mariaelisa.crestoni@uniroma1.it
Journal of the American Chemical Society
|March 12, 2010
概括
在气相研究中,紫复合物显示出有限的氧原子转移反应性. 与铁和类似物相比,它们的反应性较低,这与旋转状态影响有关.
科学领域:
- 有机金属化学 有机金属化学
- 生物有机化学 生物有机化学
- 化学物理 化学物理
背景情况:
- 金属氨酸复合物在生化和合成氧化反应中至关重要.
- 旋转状态的变化显著影响反应性,特别是在铁氨酸系统中,通常通过"两态"反应性模型来解释.
研究的目的:
- 为了研究甲复合物的气相氧原子转移化学,特别是甲 (TPFPP) 物种.
- 为了探索旋转状态变化的作用在这些复合物的反应性,与其他四牙型宏循环连接体相比.
- 描述离子物种[]和[]以及它们的反应途径.
主要方法:
- 利用电喷离子离子与富里埃变换离子循环电子共振 (FT-ICR) 质谱学相结合.
- 研究了气相氧原子转移反应[{TPFPP}Cr{III}]{+}与各种中性捐赠体.
- 研究了[{TPFPP}Cr{V}O}{+}的反应性,并使用了碰撞诱导解离 (CID) 实验.
主要成果:
- [{TPFPP}Cr{III}{+}) 与捐赠体形成了添加物,但只将氧原子转移到NO{2}中.
- 匹里丁N-氧化物添加物的碰撞诱导解离产生的[(TPFPP) Cr (((III) ] (((+) 产生的[(TPFPP) Cr ((V) O] ((+),但其他类似物没有.
- [TPFPP]Cr[V]O[+]具有有限的反应性,只能通过强大的减氧剂 (如P[OMe]3) 进行脱氧,并且通常比Fe和Mn类似物反应较低.
结论:
- 与它们的铁和对应物相比,甲复合物具有显著较低的氧原子转移反应性.
- 旋转状态效应可能是这些系统中观察到的反应性降低的原因.
- 这项研究提供了关于金属烯化学中氧原子转移的基本机制的见解.
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