Trigonal-bipyramidal geometry induced by an external water ligand in a sterically hindered iron salen complex, related to the active site of protocatechuate 3,4-dioxygenase
Trigonal-bipyramidal geometry induced by an external water ligand in a sterically hindered iron salen complex, related to the active site of protocatechuate 3,4-dioxygenase
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DOI：
10.1021/ic060650p
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发表时间：
2006-09-18
影响因子：
4.6
通讯作者：
Fujii, Hiroshi
中科院分区：
文献类型：
--
作者：
Kurahashi, Takuya;Oda, Kenji;Fujii, Hiroshi
原儿茶酸3，4双加氧酶(3，4-PCD)中非血红素铁中心的独特扭曲的三角-双锥构型被仔细研究，利用空间受阻的铁Salen络合物，很好地复制了内源性His(2)Tyr(2)供体集，以水为外部配体。一系列含bis(3，5-dimesitylsalicylidene)-1，2-dimesitylethylenediamine的铁模型化合物的X射线晶体结构表明，当水作为外部配体结合时，得到了扭曲的三角-双锥构型。铁中心从优选的正方锥体构型到扭曲的三角-双锥体构型的结构变化的程度随以CL顺序结合的外部配体而不同
A unique distorted trigonal-bipyramidal geometry observed for the non-heme iron center in protocatechuate 3,4dioxygenase (3,4-PCD) was carefully examined utilizing a sterically hindered iron salen complex, which well reproduces the endogenous His(2)Tyr(2) donor set with water as an external ligand. X-ray crystal structures of a series of iron model complexes containing bis(3,5-dimesitylsalicylidene)-1,2-dimesitylethylenediamine indicate that a distorted trigonal-bipyramidal geometry is achieved upon binding of water as an external ligand. The extent of a structural change of the iron center from a preferred square-pyramidal to a distorted trigonal-bipyramidal geometry varies with the external ligand that is bound in the order Cl