通过非黑米铁 (IV) - 氧合物复合物显著加快选择性氧原子转移:调整第一和第二协调球
Leland R Widger1, Casey G Davies, Tzuhsiung Yang
1Department of Chemistry, The Johns Hopkins University , 3400 North Charles Street, Baltimore, Maryland 21218, United States.
Journal of the American Chemical Society
|January 30, 2014
概括
一个新的铁 (II) 复合物与硫化物联体使得快速的氧原子转移反应成为可能. 这项研究详细介绍了复杂的细节.
科学领域:
- 生物有机化学 生物有机化学
- 有机金属化学 有机金属化学
- 协调化学 协调化学
背景情况:
- 铁复合物是各种氧化反应中的关键催化剂.
- 了解连接体环境在调节铁的反应性中的作用是关键.
- 新型连接体的开发可以解锁新的催化途径.
研究的目的:
- 为了合成和描述一个新的铁 (II) 复合物,其中包括硫化物联结体.
- 为了研究铁复合体在氧原子转移 (OAT) 反应中的反应性.
- 探索连接体结构对OAT机制的影响.
主要方法:
- 新型N3Py (胺) SR配体及其Fe (II) 复合物的合成.
- 关于Fe (II) 复合体及其氧化Fe (IV) 中间体的表征.
- 谱学和结构分析以确认H-结合相互作用.
- 动力学研究,以评估OAT与各种基质的活性.
主要成果:
- 一个新的Fe (II) 复合物,[Fe (II) (N3Py (Amide) SR) ] (BF4) 2 (1),被合成.
- 一种转移稳定的Fe (IV) -oxo物种,[Fe (IV) -O) -N3Py (胺) SR) ]2+) (2),产生了,具有近位胺H键供体.
- 综合体2证明了对外部硫化物基质的快速OAT.
- 实现了直接的S-氧化,产生了一种与硫氧化物结合的复合物,[Fe (II) (N3Py (Amide) S (O) R) ] (BF4) 2 (4).
- 观察到复合体1的催化OAT活性.
结论:
- 新型配体N3Py(amide) SR有效地稳定了反应性铁氧化状态.
- 氨基酸H键供体的近距离会影响Fe(IV) -oxo物种的反应性.
- 铁复合体具有作为氧化反应,特别是S-氧化反应的催化剂的潜力.
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