Tuning the Reactivity of TEMPO by Coordination to a Lewis Acid: Isolation and Reactivity of MCl3(η1‑TEMPO) (M = Fe, Al)

Addition of 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) to MCl3 (M = Fe, Al) results in the formation of MCl3(η1-TEMPO) [M = Fe (1), Al (2)]. Both 1 and 2 oxidize alcohols to generate ketones or aldehydes along with the reduced complexes MCl3(η1-TEMPOH) [M = Fe (3), Al (4)]. Complexes 1–4 were full...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2012-11, Vol.134 (47), p.19350-19353
Main Authors: Scepaniak, Jeremiah J, Wright, Ashley M, Lewis, Richard A, Wu, Guang, Hayton, Trevor W
Format: Article
Language:English
Subjects:
Alcohols - chemistry
Aldehydes - chemical synthesis
Aldehydes - chemistry
Aluminum Compounds - chemistry
Chlorides - chemistry
Crystallography, X-Ray
Cyclic N-Oxides - chemistry
Cyclic N-Oxides - isolation & purification
Ferric Compounds - chemistry
Ketones - chemical synthesis
Ketones - chemistry
Lewis Acids - chemistry
Lewis Acids - isolation & purification
Models, Molecular
Molecular Structure
Oxidation-Reduction
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Summary:Addition of 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) to MCl3 (M = Fe, Al) results in the formation of MCl3(η1-TEMPO) [M = Fe (1), Al (2)]. Both 1 and 2 oxidize alcohols to generate ketones or aldehydes along with the reduced complexes MCl3(η1-TEMPOH) [M = Fe (3), Al (4)]. Complexes 1–4 were fully characterized, including analysis by X-ray crystallography. Additionally, control experiments indicated that neither MCl3 (M = Al, Fe) nor TEMPO are capable of effecting the oxidation of alcohols independently.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja309499h