Oxidative demethylation in monooxygenase model systems. Competing pathways for binuclear and helical multinuclear copper(I) complexes
- Univ. of Groningen (Netherlands)
The ligand 2,6-bis(N-(2-pyridylethyl)formimidoyl)-1-methoxybenzene (2,6-BPB-1-OCH{sub 3}) (4) reacts with Cu-(CH{sub 3}CN){sub 4}BF{sub 4} to form novel binuclear copper(I) complexes (Cu{sub 2}(2,6-BPB-1-OCH{sub 3})(BF{sub 4}){sub 2}(CH{sub 3}CN){sub 4}) (11) and (Cu{sub 2}(2,6-BPB-1-OCH{sub 3})(BF{sub 4}){sub 2}(CH{sub 2}Cl{sub 2}){sub 0.5}) (14), or the helical polynuclear copper(I) complex (Cu(2,6-BPB-1-OCH{sub 3})(BF{sub 4})){sub n} (16). The complexes mimic certain monooxygenases as they rapidly take up O{sub 2} followed by demethylation of the anisole moiety (up to 95% yield). {sup 18}O experiments are provided that show competing aryl-oxygen ({ge}60%) and alkyl-oxygen (20%) bond cleavage pathways. Introduction of a p-methoxy substituent in the arene moiety of complex 11 decreases the oxygenation rate and led to an unprecedented O{sub 2} induced arene-OCH{sub 3}-OCD{sub 3} exchange at 20{degree}C in CD{sub 3}OD. A mechanistic rational is given.
- OSTI ID:
- 6074650
- Journal Information:
- Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 112:21; ISSN 0002-7863; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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