4.8 Article

Formation and Reactivity of a Fleeting NiIII Bisphenoxyl Diradical Species

期刊

出版社

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202211345

关键词

High-Valent Nickel Species; Oxidation States; Redox-Active Ligands; Salen Ligands

资金

  1. SERB [CRG/2019/003058]
  2. IIT Kanpur
  3. CSIR
  4. Netherlands Organisation for Scientific Research (NWO START-UP and ENW-KLEIN grants)
  5. Dutch Ministry of Education, Culture, and Science (OCW)

向作者/读者索取更多资源

Cytochrome P450s and Galactose Oxidases utilize redox active ligands to generate reactive high-valent intermediates for oxidation reactions. In this study, Ni-II(salen) was oxidized with mCPBA to produce a transient Ni-III bisphenoxyl diradical species. Spectroscopic analyses revealed oxidation events on both the ligand and the metal center, supporting the formation of the Ni-III bisphenoxyl diradical species. DFT calculations confirmed the electronic structure and d-configuration of the metal center consistent with this species. The resulting three-electron oxidized species is capable of hydrogen atom abstraction and oxygen atom transfer reactions.
Cytochrome P450s and Galactose Oxidases exploit redox active ligands to form reactive high valent intermediates for oxidation reactions. This strategy works well for the late 3d metals where accessing high valent states is rather challenging. Herein, we report the oxidation of Ni-II(salen) (salen=N,N '-bis(3,5-di-tert-butyl-salicylidene)-1,2-cyclohexane-(1R,2R)-diamine) with mCPBA (meta-chloroperoxybenzoic acid) to form a fleeting Ni-III bisphenoxyl diradical species, in CH3CN and CH2Cl2 at -40 degrees C. Electrochemical and spectroscopic analyses using UV/Vis, EPR, and resonance Raman spectroscopies revealed oxidation events both on the ligand and the metal centre to yield a Ni-III bisphenoxyl diradical species. DFT calculations found the electronic structure of the ligand and the d-configuration of the metal center to be consistent with a Ni-III bisphenoxyl diradical species. This three electron oxidized species can perform hydrogen atom abstraction and oxygen atom transfer reactions.

作者

我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。

评论

主要评分

4.8
评分不足

次要评分

新颖性
-
重要性
-
科学严谨性
-
评价这篇论文

推荐

暂无数据
暂无数据