Formation and Reactivity of a Fleeting NiIII Bisphenoxyl Diradical Species

Ayushi Awasthi, Isaac F. Leach, Silène Engbers, Rakesh Kumar, Raju Eerlapally, Sikha Gupta, Johannes E. M. N. Klein*, Apparao Draksharapu*

*Corresponding author voor dit werk

OnderzoeksoutputAcademicpeer review

13 Citaten (Scopus)
54 Downloads (Pure)


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 NiII(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 NiIII bisphenoxyl diradical species, in CH3CN and CH2Cl2 at −40 °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 NiIII 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 NiIII bisphenoxyl diradical species. This three electron oxidized species can perform hydrogen atom abstraction and oxygen atom transfer reactions.

Originele taal-2English
Aantal pagina's6
TijdschriftAngewandte Chemie - International Edition
Nummer van het tijdschrift41
StatusPublished - 10-okt.-2022


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