Publication
Title
A pulsed EPR and DFT investigation of the stabilization of coordinated phenoxyl radicals in a series of cobalt Schiff-base complexes
Author
Abstract
We recently demonstrated how the aerobic addition of acetic acid to N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-diamino CoII, [Co(1)], leads to the formation of an unusual coordinated CoIII-phenoxyl radical. In this work, some of the structural aspects associated with the Schiff-base-derived ligand (1) that are crucial for the acid-mediated formation of the phenoxyl radical are investigated. For comparison with [Co(1)], we therefore studied the influence of acetic acid on two complexes: (1) the N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-ethane-diamino CoII complex, [Co(2)], that lacks the cyclohexyl group of [Co(1)], and (2) the N′-disalicylidene-ethylenediamine CoII salen complex, [Co(3)], that lacks both the tertiary butyl groups and the cyclohexyl groups. It is shown that the cyclohexyl group of [Co(1)] is not involved in the formation or stabilization of the phenoxyl radical, whereas the tertiary butyl groups of [Co(1)] play a crucial role. In addition, the characteristics of the phenoxyl radical, formed after aerobic addition of acetic acid to [Co(2)], are analyzed in detail by pulsed electron paramagnetic resonance, in combination with isotopic labeling. The experimental data are compared to density functional theory computations and to previous data on the acid-mediated phenoxyl radical of [Co(1)].
Language
English
Source (journal)
Applied magnetic resonance. - Stuttgart
Publication
Stuttgart : 2010
ISSN
0937-9347
Volume/pages
37:1/4(2010), p. 289-303
ISI
000272173500022
Full text (Publisher's DOI)
UAntwerpen
Faculty/Department
Research group
Publication type
Subject
Affiliation
Publications with a UAntwerp address
External links
Web of Science
Record
Identification
Creation 09.02.2010
Last edited 19.06.2017
To cite this reference