基和H2通过[Fe]-H2酶模型复合物的激活
Xuan Zhao1, Chao-Yi Chiang, Matthew L Miller
1Department of Chemistry, Texas A&M University, College Station 77843, USA.
Journal of the American Chemical Society
|January 9, 2003
概括
这项研究表明,基于铁的酶 (H2ase) 模型可以同时激活二和基. 双核铁复合物与合联体对于这种催化活性至关重要.
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.
- 生物有机化学 生物有机化学
背景情况:
- 已知铁酶 (H2ase) 模型复合体可以激活二 (H2).
- 桥接化物种 (微-H) ((微-pdt) [Fe ((CO) 2 ((PMe3)) ]2+ (1-H+) 呈现出与H2/D2和H2/D2O混合物的H/D杂乱.
研究的目的:
- 为了研究由[Fe]H2酶模型复合体同时激活基和H2.
- 探索双核合联体在催化活性和稳定性中的作用.
主要方法:
- 铁复合物的光解产生开放的协调点.
- 气 (D2) 和各种基之间的催化H/D交换反应.
- 介质和产品的结构性表征.
- 双核催化剂与单牙催化剂的比较.
主要成果:
- 复杂的1-H+及其EDT模拟物催化了D2与终端基 (乙烯,,1-布) 之间的H/D交换,但不包括较大的基.
- 观察到在内部的乙烯基中对H/D交换有相当大的区域选择性.
- 双核合配体 (pdt,edt) 对于催化剂的稳定性和活性至关重要;单牙类型的类似物被分解.
- 形成了S-基化产品,对H2无反应,表明它们不在催化途径上.
结论:
- 提出了一种机制,该机制涉及olefin与开放部位结合并形成Fe- ((CH2CHDR) 中间体.
- 由S-XXX-S连接体提供的双核酸盐效应对于这些[Fe]H2酶模型的活性至关重要.
- 这些发现为在活性[Fe]H2ase.中独特的S-XXX-S辅因子的功能提供了洞察力.
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