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首页> 外文期刊>Polyhedron: The International Journal for Inorganic and Organometallic Chemistry >Synthesis and characterization of a monomeric and a dihydroxo-bridged dimeric complexes of iron(III) with alpha-benzoinoxime
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Synthesis and characterization of a monomeric and a dihydroxo-bridged dimeric complexes of iron(III) with alpha-benzoinoxime

机译：铁（III）与α-苯并肟的单体和二氢桥联二聚体的合成与表征

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摘要

The reaction of alpha-benzoinoxime, H2BNO with FeCl3 in the presence of Et3N as a base gives the mononuclear Fe(III) complex, Fe(HBNO)(3) (1). Treatment of 1 with a methanolic solution of KOH at room temperature leads to a dinuclear Fe(III)-Fe(III) complex, [Fe(HBNO)(2)OH](2) (2). The complexes were initially characterized on the basis of their elemental, mass and thermal analyses. The IR studies were useful in assigning the coordination mode of the benzoinoxime ligand to the iron metal. In addition, the presence of a hydroxo-bridge in the dimeric complex 2 is inferred from the IR spectral studies. Room-temperature Mossbauer studies indicated octahedral, high-spin iron(III). Variable-temperature magnetic susceptibility measurements supported the existence of the mu-dihydroxo-bridging structure core, Fe-III(mu-OH)(2)Fe-III in the dinuclear complex 2. Theoretical modelling of the magnetic data indicated a weak antiferromagnetic spin exchange between the iron(III) centers (J = -8.35 cm(-1), g = 2.01, p = 0.02 and TIP = 1.7 x 10(-4) cm(3) mol(-1) for H = -2JS(1) . S-2). The electronic spectra of the complexes revealed two bands due to d-d transitions and one band assignable to an oxygen (p(pi)) -> Fe(d(pi*)) LMCT transition observed in each complex. An additional charge-transfer transition, assignable to mu-hydroxo(p(pi)) -> Fe(d(pi*)), was observed for the dimeric complex 2. The structural and vibrational behaviors of these complexes have been elucidated with quantum mechanical methods. (c) 2006 Elsevier Ltd. All rights reserved.
机译：在以Et3N为碱的情况下，α-苯并肟，H2BNO与FeCl3的反应生成单核Fe（III）配合物Fe（HBNO）（3）（1）。在室温下用KOH的甲醇溶液处理1会生成双核Fe（III）-Fe（III）络合物[Fe（HBNO）（2）OH]（2）（2）。最初根据元素，质量和热分析对复合物进行表征。 IR研究对于将苯并氧肟肟配体配位给铁金属是有用的。另外，由IR光谱研究推断二聚配合物2中羟基桥的存在。 Mossbauer室温研究表明，八面体高自旋铁（III）。可变温度磁化率测量结果支持了在双核络合物2中存在mu-dihydroxo-架桥结构核心Fe-III（mu-OH）（2）Fe-III。磁性数据的理论建模表明弱的反铁磁自旋铁（III）中心之间的交换（J = -8.35 cm（-1），g = 2.01，p = 0.02和TIP = 1.7 x 10（-4）cm（3）mol（-1），H = -2JS （1）.S-2）。配合物的电子光谱揭示了由于d-d跃迁而产生的两个谱带，以及在每个配合物中观察到的可分配给氧（p（pi））-> Fe（d（pi *））LMCT跃迁的谱带。对于二聚体复合物2，观察到了一个附加的电荷转移跃迁，可分配给mu-hydroxo（p（pi））→Fe（d（pi *））。这些复合物的结构和振动行为已通过量子得以阐明。机械方法。 （c）2006 Elsevier Ltd.保留所有权利。

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