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Electronic Structure Evaluation of an Oxidized Tris(methoxy)‐Substituted Ni Salen Complex
Author(s) -
Chiang Linus,
Clarke Ryan M.,
Herasymchuk Khrystyna,
Sutherland Mathew,
Prosser Kathleen E.,
Shimazaki Yuichi,
Storr Tim
Publication year - 2016
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201501144
Subject(s) - chemistry , ligand (biochemistry) , substituent , electrochemistry , cyclohexane , diamine , nickel , resonance (particle physics) , ring (chemistry) , radical ion , photochemistry , raman spectroscopy , electron paramagnetic resonance , stereochemistry , crystallography , polymer chemistry , organic chemistry , nuclear magnetic resonance , ion , biochemistry , physics , receptor , electrode , particle physics , optics
The Ni salen complex N , N′ ‐bis(2,3,4‐trimethoxysalicylidene)‐1,2‐cyclohexane‐(1 R ,2 R )‐diamine nickel(II) ( 1 ), containing ortho ‐, meta ‐, and para ‐methoxy‐substituted phenolate moieties, was prepared. Electrochemical studies revealed that the first oxidation of 1 occurs at a similar potential to a previously reported Ni salen complex NiSal t Bu,OMe , employing an ortho ‐ t Bu and para ‐methoxy substitution pattern (M. Orio et al., Angew. Chem. Int. Ed. 2010 , 49 , 4989), demonstrating the counteracting effects of the methoxy substituent depending on ring location ( ortho / para vs. meta ). The second oxidation occurred at a much lower potential ( E 1/2 2 – E 1/2 1 = 0.11 V) for 1 , in comparison to NiSal t Bu,OMe , suggesting significant localization of the ligand radical. The one‐electron oxidized form was prepared and studied using a number of experimental and theoretical methods. A localized ligand radical electronic structure was confirmed by the shape and intensity of the NIR bands, which was further verified by the presence of both phenolate and phenoxyl signatures in the resonance Raman spectrum. Theoretical calculations provided insight into the degree of ligand radical localization, and the nature of the low energy bands observed in the Vis/NIR experiment. Overall, the oxidation of 1 results in a localized ligand radical complex, with further oxidation processes easily accessible due to resonance stabilization afforded by the methoxy substituents.