Biomimetic high-valent non-heme iron oxidants for the cis-dihydroxylation and epoxidation of olefins

被引:117
作者
Bautz, Jochen [1 ]
Comba, Peter [1 ]
de laorden, Carlos Lopez [1 ]
Menzel, Matthias [1 ]
Rajaraman, Gopalan [1 ]
机构
[1] Heidelberg Univ, Inst Anorgan Chem, INF 270, D-69120 Heidelberg, Germany
关键词
dihydroxylation; epoxidation; iron; oxidation; reaction mechanisms;
D O I
10.1002/anie.200701681
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Pathfinding: The iron(II) complex of the bispidine ligand L1 is oxidized with H2O2 to intermediate-spin [(L 1)FeIVOH)2]2+ (1, see picture) which forms eis diols 2 from olefins, and the high-spin [(L1)Fe IV=O(OH2)]2+ ferryl complex (3) results in epoxidation (4). Product distributions (diol/epoxide) and 18O labeling studies are used to propose a mechanism, which is fully supported by DFT analyses. (Figure Presented). © 2007 Wiley-VCH Verlag GmbH & Co. KGaA.
引用
收藏
页码:8067 / 8070
页数:4
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