A diiron center stabilized by a bis-TPA ligand as a model of soluble methane monooxygenase:: Predominant alkene epoxidation with H2O2
A diiron center stabilized by a bis-TPA ligand as a model of soluble methane monooxygenase:: Predominant alkene epoxidation with H2O2
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DOI：
10.1002/anie.200501825
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发表时间：
2005-01-01
影响因子：
16.6
通讯作者：
Reglier, M
中科院分区：
文献类型：
--
作者：
Kodera, M;Itoh, M;Reglier, M
可溶甲烷单加氧酶(SMMO)的模型[1]可用于研究氧活化的过氧二铁(III)和氧二铁(IV)中间体，[1]以及开发有效的氧化催化剂。[2]我们为获得双金属生物载体模型所做的努力得到了一系列双核多吡啶配体。[3]六吡啶配体的二铁络合物有效地催化烷烃的氧化，并形成热稳定的过氧络合物。三(2-吡啶甲基)胺(TPA)和相关配体的[3D-f]二铁络合物是已知的有效的sMMO模型。然而，这些配体在溶液中并不稳定双核铁。[6，7]TPA衍生物的铁络合物催化烯烃与H_2O_2氧化生成1，2-顺式二醇和环氧化物，并提出了Rieske双加氧酶类型的单铁活性物种。[6]然而，与TPA相似的N，N‘-二甲基-N，N’-双(2-吡啶甲基)乙烷-1，2-二胺(MEP)的铁络合物观察到了主要的环氧化反应，因此提出了sMMO类型的二铁物种。我们合成了1，2-双[2-{双(2-吡啶甲基)氨甲基}-6-吡啶]乙烷(6-HPA)作为双-TPA脱核配体。在这里，我们描述了6-HPA的二铁配合物的合成、结构及其作为一种非常有用的sMMO模型的应用。该络合物可催化环氧化反应
Models of soluble methane monooxygenase (sMMO)[1] are useful for studying peroxodiiron (iii) and oxodiiron (iv) intermediates in OÀO activation,[1] as well as for developing an efficient oxidation catalyst.[2] Our synthetic efforts to obtain models for dimetal biosites yielded a series of dinucleating polypyridine ligands.[3] The diiron complex of the hexapyridine ligand efficiently catalyzes the oxidation of alkanes and forms a thermally stable peroxo complex.[3d–f] Diiron complexes of tris (2-pyridylmethyl) amine (TPA) and related ligands are known as effective sMMO models.[4] However, such ligands do not stabilize the diiron core in solution,[5] and the resulting complexes display varied reactivity, depending on them being mono-or diiron complexes.[6, 7] Iron complexes of TPA derivatives catalyze alkene oxidation with H2O2 to give the 1, 2-cis-diol and epoxide, and Rieske dioxygenasetype monoiron active species have been proposed.[6] However, predominant epoxidation was observed with the iron complex of the ligand N, N’-dimethyl-N, N’-bis (2-pyridylmethyl) ethane-1, 2-diamine (MEP), which is similar to TPA, and an sMMO-type diiron species was proposed.[7] Therefore, a TPA-containing dinucleating ligand capable of stabilizing a diiron core in solution would be useful for the development of an effective sMMO model.We prepared 1, 2-bis [2-{bis (2-pyridylmethyl) aminomethyl}-6-pyridyl] ethane (6-HPA) as a bis-TPA dinucleating ligand. Herein, we describe the synthesis, structure, and application of the diiron complex of 6-HPA as a highly useful sMMO model. The complex can catalyze epoxidation with