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含某些酸腙和2,2'-联吡啶的氧钒(IV)三元配合物的合成与光谱表征

Synthesis and spectral characterization of ternary complexes of oxovanadium(IV) containing some acid hydrazones and 2,2'-bipyridine.

作者信息

Sreeja P B, Kurup M R Prathapachandra

机构信息

Department of Applied Chemistry, Cochin University of Science & Technology, Kochi 682 022, India.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2005 Jan 1;61(1-2):331-6. doi: 10.1016/j.saa.2004.04.001.

Abstract

An interesting series of heterocyclic base adducts of oxovanadium(IV) complexes have been synthesized by the reaction of vanadium(IV) oxide acetylacetonate with some hydrazones (H(2)L) in the presence of a heterocyclic base 2,2'-bipyridine. The compounds were characterized by analytical and different physico-chemical techniques like IR, electron paramagnetic resonance (EPR) and UV-Vis spectral studies and magnetic studies. The EPR spectra indicate that the free electron is in the d(xy) orbital. The coordination geometry around oxovanadium(IV) in all complexes is octahedral, with one dibasic tridentate ligand L(2-), and one bidentate heterocyclic base. The IR spectra suggest that coordination takes place through azomethine nitrogen and enolate oxygen from the hydrazide moiety and phenolate oxygen. The pyridyl nitrogens of the hydrazones, H(2)L(2) and H(2)L(4) are not involved in the coordination. The molar conductivities show that all the complexes are non-electrolytes. All electronic transitions were assigned. All the compounds are paramagnetic. EPR studies of all compounds suggest axial symmetry. The calculated bonding parameters indicate that in-plane sigma bonding is more covalent than in-plane pi bonding.

摘要

通过乙酰丙酮氧钒(IV)与一些腙(H₂L)在杂环碱2,2'-联吡啶存在下反应,合成了一系列有趣的氧钒(IV)配合物的杂环碱加合物。通过分析和不同的物理化学技术如红外光谱、电子顺磁共振(EPR)、紫外可见光谱研究和磁性研究对这些化合物进行了表征。EPR光谱表明自由电子在d(xy)轨道上。所有配合物中氧钒(IV)周围的配位几何形状为八面体,有一个二价三齿配体L²⁻和一个双齿杂环碱。红外光谱表明配位通过酰肼部分的偶氮甲碱氮和烯醇氧以及酚氧发生。腙H₂L₂和H₂L₄的吡啶基氮不参与配位。摩尔电导率表明所有配合物都是非电解质。所有电子跃迁都已归属。所有化合物都是顺磁性的。所有化合物的EPR研究表明具有轴向对称性。计算得到的键参数表明面内σ键比面内π键更具共价性。

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