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

被引:85
作者
Scepaniak, Jeremiah J. [1 ]
Wright, Ashley M. [1 ]
Lewis, Richard A. [1 ]
Wu, Guang [1 ]
Hayton, Trevor W. [1 ]
机构
[1] Univ Calif Santa Barbara, Dept Chem & Biochem, Santa Barbara, CA 93106 USA
基金
美国国家科学基金会;
关键词
CATALYZED AEROBIC OXIDATION; RADICAL MOLECULAR-COMPLEXES; COUPLED ELECTRON-TRANSFER; PRIMARY ALCOHOLS; MILD CONDITIONS; IONIC LIQUID; ALDEHYDES; EFFICIENT; HALIDES; KETONES;
D O I
10.1021/ja309499h
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Addition of 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) to MCl3 (M = Fe, Al). results in the formation of MCl3(eta(1)-TEMPO). [M = Fe (1), Al (2)] Both 1 and 2:oxidize alcohols to. generate ketones or aldehydes 'along' with the reduced complexes MCl3(eta(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 MCl3 (M = Al, Fe)nor, TEMPO are capable of effecting the Oxidation:of alcohols independently.
引用
收藏
页码:19350 / 19353
页数:4
相关论文
共 49 条
[1]   Iron-mediated cleavage of coordinated 1,1,1,5,5,5-hexafluoropentane-2,4-dione by the 2,2,6,6-tetramethylpiperidine-1-oxyl nitroxyl radical [J].
Ahlers, C ;
Dickman, MH .
INORGANIC CHEMISTRY, 1998, 37 (24) :6337-6340
[2]  
[Anonymous], CAMBRIDGE STRUCTURAL
[3]   TEMPO-catalyzed aerobic oxidation of alcohols to aldehydes and ketones in ionic liquid [bmim][PF6] [J].
Ansari, IA ;
Gree, R .
ORGANIC LETTERS, 2002, 4 (09) :1507-1509
[4]   Cu(bipy)2+/TEMPO-Catalyzed Oxidation of Alcohols: Radical or Nonradical Mechanism? [J].
Belanzoni, Paola ;
Michel, Carine ;
Baerends, Evert Jan .
INORGANIC CHEMISTRY, 2011, 50 (23) :11896-11904
[5]   Selective aerobic oxidation of alcohols with a combination of a polyoxometalate and nitroxyl radical as catalysts [J].
Ben-Daniel, R ;
Alsters, P ;
Neumann, R .
JOURNAL OF ORGANIC CHEMISTRY, 2001, 66 (25) :8650-8653
[6]  
Bill E., 2008, JULX VERSION 1 4 1
[7]   BOND-DISSOCIATION ENERGIES IN DMSO RELATED TO THE GAS-PHASE [J].
BORDWELL, FG ;
CHENG, JP ;
JI, GZ ;
SATISH, AV ;
ZHANG, XM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (26) :9790-9795
[8]  
Boudreaux E.A., 1976, Theory and Applications of Molecular Paramagnetism
[9]   Capture of NO by a Frustrated Lewis Pair: A New Type of Persistent N-Oxyl Radical [J].
Cardenas, Allan Jay P. ;
Culotta, Brooks J. ;
Warren, Timothy H. ;
Grimme, Stefan ;
Stute, Annika ;
Froehlich, Roland ;
Kehr, Gerald ;
Erker, Gerhard .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2011, 50 (33) :7567-7571
[10]   Efficient Mn-Cu and Mn-Co-TEMPO-catalysed oxidation of alcohols into aldehydes and ketones by oxygen under mild conditions [J].
Cecchetto, A ;
Fontana, F ;
Minisci, F ;
Recupero, F .
TETRAHEDRON LETTERS, 2001, 42 (38) :6651-6653