Characterization and Reactivity of a Tetrahedral Copper(II) Alkylperoxido Complex.
In: Chemistry - A European Journal, Jg. 25 (2019-08-22), Heft 47, S. 11157-11165
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Zugriff:
A tetrahedral CuII alkylperoxido complex [CuII(TMG3tach)(OOCm)]+ (1OOCm) (TMG3tach={2,2′,2′′‐[(1s,3s,5s)‐cyclohexane‐1,3,5‐triyl]tris‐(1,1,3,3‐tetramethyl guanidine)}, OOCm=cumyl peroxide) is prepared and characterized by UV/Vis, cold‐spray ionization mass spectroscopy (CSI‐MS), resonance Raman, and EPR spectroscopic methods. Product analysis of the self‐decomposition reaction of 1OOCm in acetonitrile (MeCN) indicates that the reaction involves O−O bond homolytic cleavage of the peroxide moiety with concomitant C−H bond activation of the solvent molecule. When an external substrate such as 1,4‐cyclohexadiene (CHD) is added, the O−O bond homolysis leads to C−H activation of the substrate. Furthermore, the reaction of 1OOCm with 2,6‐di‐tert‐butylphenol derivatives produces the corresponding phenoxyl radical species (ArO.) together with a CuI complex through a concerted proton‐electron transfer (CPET) mechanism. Details of the reaction mechanisms are explored by DFT calculations. [ABSTRACT FROM AUTHOR]
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Titel: |
Characterization and Reactivity of a Tetrahedral Copper(II) Alkylperoxido Complex.
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Autor/in / Beteiligte Person: | Shimizu, Ikuma ; Morimoto, Yuma ; Velmurugan, Gunasekaran ; Gupta, Tulika ; Paria, Sayantan ; Ohta, Takehiro ; Sugimoto, Hideki ; Ogura, Takashi ; Comba, Peter ; Itoh, Shinobu |
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Zeitschrift: | Chemistry - A European Journal, Jg. 25 (2019-08-22), Heft 47, S. 11157-11165 |
Veröffentlichung: | 2019 |
Medientyp: | academicJournal |
ISSN: | 0947-6539 (print) |
DOI: | 10.1002/chem.201902669 |
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