Synthesis and reactivity of a 4His enzyme model complex.
Synthesis and reactivity of a 4His enzyme model complex.
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4His 酶模型复合物的合成和反应性。
DOI：
10.1039/c7ra09456f
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发表时间：
2017
期刊：
影响因子：
3.9
通讯作者：
Chavez,FermanA
中科院分区：
文献类型：
--
作者：
Li,Jia;Banerjee,Atanu;Hasse,TimothyA;Loloee,Reza;Biros,ShannonM;Staples,RichardJ;Chavez,FermanA
一种新的铁（II）配合物已制备和表征。[Fe（TrIm）4（OTf）2]（1，TrIm = 1-三苯甲基咪唑）。用X射线晶体学方法测定了1的固态结构。化合物1属于三斜晶系，空间群为P，a = 13.342（7）B = 13.5131（7），c = 13.7025（7）。铁中心存在于扭曲的八面体几何结构中，与四个赤道咪唑基团和两个轴向三氟甲磺酸酯氧基团协调。变场变温磁性测量表明，该配合物在20 K ~ 300 K之间具有高自旋。磁测数据的拟合结果为g = 2.24，D =-0.80 cm-1。对于1存在大的HOMO-LUMO带隙能量（3.89eV），表明高稳定性。向1中加入H2 O2或tBuOOH导致形成含氧中间体，其在分解时导致咪唑配体上的三苯甲基取代基氧化。
A new iron(II) complex has been prepared and characterized. [Fe(TrIm)4(OTf)2] (1, TrIm = 1-tritylimidazole). The solid state structure of 1 has been determined by X-ray crystallography. Compound 1 crystallizes in triclinic space group P, with a = 13.342(7) Å, b = 13.5131(7) Å and c = 13.7025(7) Å. The iron center resides in distorted octahedral geometry coordinated to four equatorial imidazole groups and two axial triflate oxygens groups. The complex is high spin between 20 K and 300 K as indicated by variable field variable temperature magnetic measurements. A fit of the magnetic data yielded g = 2.24 and D = −0.80 cm−1. A large HOMO–LUMO gap energy (3.89 eV) exists for 1 indicating high stability. Addition of H2O2 or tBuOOH to 1 results in formation of an oxygenated intermediate which upon decomposition results in oxidation of the trityl substituent on the imidazole ligand.