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1-苯并三唑-1-基-1-[(对-X-苯基)腙基]丙酮铁(III)配合物的合成与光谱研究

Synthesis and spectroscopic studies on iron(III) complexes of 1-benzotriazol-1-yl-1-[(p-X-phenyl)hydrazono]propan-2-one.

作者信息

El-Dissouky Ali, Al-Awadi Nouria A, Shauib Nadia M, Abbas Alaa B

机构信息

Faculty of Science, Chemistry Department, Kuwait University, Safat 13060, Kuwait.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2007 Jul;67(3-4):1072-9. doi: 10.1016/j.saa.2006.09.026. Epub 2006 Oct 4.

Abstract

A new series of iron(III) complexes are synthesized from the reaction of the polyfunctional ligands 1-benzotriazol-1-yl-1-[p-X-phenyl]hydrazono]propan-2-one (X=H, Cl, NO(2), CH(3) or OCH(3) corresponding to HL(1),HL(2), HL(3), HL(4) or HL(5), respectively, with iron(III) chloride in the presence of LiOH by the conventional and microwave induced energy methods. The conventional method led to the formation of [FeL(3)].nH(2)O but the microwave induced energy gave [FeLCl(2)], n=1-3 and L is the anion of HL(1)-HL(5). The complexes are characterized by the elemental analysis, molar conductivity, magnetic and spectral (FT-IR, UV-vis and ESR) studies. The magnetic and spectral studies showed that [FeLCl(2)] are polymeric octahedral, [Fe(L(1))(3)].H(2)O is a low spin octahedral and (d(xz),d(yz))(4) (d(xy))(1) ground state, [FeL(3)].nH(2)O, L=anion of HL(4) or HL(5) and are octahedral with intermediate spin (S=32) with ground state (d(xy))(2)(d(xz),d(yz))(3) electronic configuration while for the anions of HL(2) and HL(3), they have (t(2g))(3)(e(g))(5) admixed with (d(xy))(2)(d(xz),d(yz))(3) configurations. From the ESR data, the contribution of the high spin (S=52) and low spin (S=32) to the quantum mechanical spin intermediate (QMS), and the crystal field parameters Delta and V are calculated and related to the electronic and steric effects of the ligands. The electronic spectral data confirm that obtained from the ESR, and the different ligand field parameters as well as the pi-->t(2g), t(2g)-->e(g), e(g)-->pi*, pi-->pi* transitions are estimated and compared with that experimentally obtained.

摘要

通过传统方法和微波诱导能量法,在氢氧化锂存在下,使多功能配体1-苯并三唑-1-基-1-[对-X-苯基]肼基]丙酮(X = H、Cl、NO₂、CH₃或OCH₃,分别对应HL₁、HL₂、HL₃、HL₄或HL₅)与氯化铁反应,合成了一系列新的铁(III)配合物。传统方法得到了[FeL₃]·nH₂O,但微波诱导能量法得到了[FeLCl₂],n = 1 - 3,且L是HL₁ - HL₅的阴离子。通过元素分析、摩尔电导率、磁性和光谱(傅里叶变换红外光谱、紫外可见光谱和电子顺磁共振光谱)研究对配合物进行了表征。磁性和光谱研究表明,[FeLCl₂]是聚合八面体结构,[Fe(L₁)₃]·H₂O是低自旋八面体结构且基态为(d(xz),d(yz))⁴(d(xy))¹,[FeL₃]·nH₂O,L = HL₄或HL₅的阴离子,是具有中间自旋(S = 3/2)且基态电子构型为(d(xy))²(d(xz),d(yz))³的八面体结构,而对于HL₂和HL₃的阴离子,它们具有(t₂g)³(e g)⁵并混合(d(xy))²(d(xz),d(yz))³构型。根据电子顺磁共振光谱数据,计算了高自旋(S = 5/2)和低自旋(S = 3/2)对量子力学自旋中间体(QMS)的贡献以及晶体场参数Δ和V,并将其与配体的电子效应和空间效应相关联。电子光谱数据证实了从电子顺磁共振光谱得到的结果,并估算了不同的配体场参数以及π→t₂g、t₂g→e g、e g→π*、π→π*跃迁,并与实验得到的结果进行了比较。

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