O2 activation by nonheme iron complexes:: A monomeric Fe(III)-oxo complex derived from O2
O2 activation by nonheme iron complexes:: A monomeric Fe(III)-oxo complex derived from O2
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DOI：
10.1126/science.289.5481.938
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发表时间：
2000-08-11
期刊：
影响因子：
56.9
通讯作者：
Borovik, AS
中科院分区：
文献类型：
--
作者：
MacBeth, CE;Golombek, AP;Borovik, AS
末端含氧配体的铁是几种合成和生化催化循环的关键中间体。然而，关于这些类型的配合物的结构信息缺乏，因为它们的不稳定性阻碍了在环境条件下的隔离。本文报道了直接由二氧（O-2）衍生的末端氧配体的铁（III）配合物的分离和结构表征。将氧铁单元置于有氢键基团的合成腔内，形成稳定的结构。空腔在铁中心周围创造了一个微环境，有助于调节O-2的激活和稳定氧铁单元。这些空腔与金属蛋白的活性位点具有相同的特性，其功能与位点结构密切相关。
Iron species with terminal oxo Ligands are implicated as key intermediates in several synthetic and biochemical catalytic cycles. However, there is a dearth of structural information regarding these types of complexes because their instability has precluded isolation under ambient conditions. The isolation and structural characterization of an iron(III) complex with a terminal oxo Ligand, derived directly from dioxygen (O-2), is reported. A stable structure resulted from placing the oxoiron unit within a synthetic cavity Lined with hydrogen-bonding groups. The cavity creates a microenvironment around the iron center that aids in regulating O-2 activation and stabilizing the oxoiron unit. These cavities share properties with the active sites of metalloproteins, where function is correlated strongly with site structure.