在 [CoIII(TAML) ]0/-复合体中影响烯形成的连接基氧化无罪
Nicolaas P van Leest, Martijn A Tepaske, Jean-Pierre H Oudsen
1Department of Chemistry , Johns Hopkins University , Baltimore , Maryland 21218 , United States.
在-TAML复合体中证实了胺宏环联体 (TAML) 的氧化还原无害性. 这项研究揭示了氧化-TAML中的联结基,对于催化转移反应至关重要.
科学领域:
- 无机化学
- 有机金属化学
- 光谱学
- 计算化学
背景情况:
- 自2006年以来,复合体中的四胺宏环联体 (TAML) 支架的氧化还原行为一直受到争议.
- 了解配体氧化还原非无罪对于阐明催化反应机制至关重要.
研究的目的:
- 为了最终证明-复合体中TAML骨干的氧化还原无害性.
- 描述氧化-TAML物种的电子结构及其在转移反应中的作用.
主要方法:
- 使用各种光谱技术 (EPR,XANES,UV-vis) 来进行表征.
- 使用高分辨率质谱和磁矩测量.
- 执行多引用 (CASSCF) 计算以确定电子结构.
主要成果:
- 证实 anionic -TAML 复合体中的 TAML 骨干是无氧化,在一电子氧化时形成联体中心基.
- 氧化复合体的电子结构是由S=1中心与基结合而产生的双体 (S=1/2).
- 与基前体 (PhINNs) 的反应导致TAML中心的氧化,形成基复合物 ([Co(TAML) ((NNs)) 和[Co(TAML) ((NNs))),对催化转移至关重要.
结论:
- 复合体中的TAML连接体表现出显著的氧化还原无罪性,作为氧化还原活性成分.
- 这些-TAML复合体介导的催化转移机制中的关键中间体是以为中心的基因.
- TAML联体的氧化还原状态决定了单或双基复合物的形成.
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