The reactivity of well defined diiron(III) peroxo complexes toward substrates: Addition to electrophiles and hydrocarbon oxidation

被引:25
作者
LeCloux, DD [1 ]
Barrios, AM [1 ]
Lippard, SJ [1 ]
机构
[1] MIT, Dept Chem, Cambridge, MA 02139 USA
基金
美国国家科学基金会;
关键词
biomimetic reactions; oxygen; oxygenation;
D O I
10.1016/S0968-0896(98)00270-3
中图分类号
Q5 [生物化学]; Q7 [分子生物学];
学科分类号
071010 ; 081704 ;
摘要
The reactivity of previously reported peroxo adducts [Fe(mu-O-2)(mu-L)(O2CPhCy)(2)(1-Bu-Im)(2)] (1), and [Fe(mu-O-2)(mu-L) (O2CPhCy)(2)(py)(2)] (2), where L is a dinucleating ligand based on the m-xylylenediamine bis(Kemp's triacid imide), toward a variety of substrates is described. These studies were performed to probe the electronic properties of 1 and 2 and evaluate their potential as selective hydrocarbon oxidants. Compound 1 is nucleophilic at -77 degrees C, reacting with phenols and carboxylic acids to liberate hydrogen peroxide, whereas the less electron-rich pyridine analogue 2 is unreactive toward both reagents. By contrast, neither reacts at -77 degrees C with electrophilic reagents such as olefins or triphenylphosphine, or with weak hydrogen atom donors such as dimethylbenzylamine. When solutions of 1 are warmed to room temperature in solvents such as THF, toluene, and cyclopentane, mixtures of alcohol and ketone products derived from the solvent are formed. A detailed investigation of cyclopentane oxidation strongly points to a radical autoxidation pathway. These results are discussed in the context of the selective hydroxylation chemistry that occurs at the carboxylate-bridged diiron centers in soluble methane monooxygenase. (C) 1999 Elsevier Science Ltd. All rights reserved.
引用
收藏
页码:763 / 772
页数:10
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