title: Tuning the reactivity of TEMPO by coordination to a Lewis acid: isolation and reactivity of MCl3(η1-TEMPO) (M = Fe, Al).
abstract: Addition of 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) to MCl(3) (M = Fe, Al) results in the formation of MCl(3)(η(1)-TEMPO) [M = Fe (1), Al (2)]. Both 1 and 2 oxidize alcohols to generate ketones or aldehydes along with the reduced complexes MCl(3)(η(1)-TEMPOH) [M = Fe (3), Al (4)]. Complexes 1-4 were fully characterized, including analysis by X-ray crystallography. Additionally, control experiments indicated that neither MCl(3) (M = Al, Fe) nor TEMPO are capable of effecting the oxidation of alcohols independently.
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, USA.
authors.forename: Jeremiah J
authors.initials: JJ
authors.lastname: Scepaniak
authors.forename: Ashley M
authors.initials: AM
authors.lastname: Wright
authors.forename: Richard A
authors.initials: RA
authors.lastname: Lewis
authors.forename: Guang
authors.initials: G
authors.lastname: Wu
authors.forename: Trevor W
authors.initials: TW
authors.lastname: Hayton
mesh_terms: D000438:Alcohols / Q000737:chemistry; D000447:Aldehydes / Q000138:chemical synthesis / Q000737:chemistry; D000077410:Aluminum Chloride; D017607:Aluminum Compounds / Q000737:chemistry*; D002712:Chlorides / Q000737:chemistry*; D018360:Crystallography, X-Ray; D003497:Cyclic N-Oxides / Q000737:chemistry* / Q000302:isolation & purification; D005290:Ferric Compounds / Q000737:chemistry*; D007659:Ketones / Q000138:chemical synthesis / Q000737:chemistry; D058116:Lewis Acids / Q000737:chemistry* / Q000302:isolation & purification; D008958:Models, Molecular; D015394:Molecular Structure; D010084:Oxidation-Reduction
chemical_list: D000438:Alcohols; D000447:Aldehydes; D017607:Aluminum Compounds; D002712:Chlorides; D003497:Cyclic N-Oxides; D005290:Ferric Compounds; D007659:Ketones; D058116:Lewis Acids; D000077410:Aluminum Chloride; C024555:ferric chloride; C003959:TEMPO