Stereospecific formation of vanadium mandelato complexes with [Fe(2,2′-bipyridine)3]2+ as a counter ion

IF 1.6 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Transition Metal Chemistry Pub Date : 2023-08-01 DOI:10.1007/s11243-023-00543-w

Peter Schwendt, Róbert Gyepes, Jozef Tatiersky, Juraj Filo, Marek Bujdoš, Dominika Zákutná, Lukáš Krivosudský

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Abstract

Two vanadium complexes of mandelic acid having [Fe(bpy)₃]²⁺ as counterion, [Fe(bpy)₃][V₂O₄(rac-mand)₂]·4.9H₂O·0.1CH₃CN (1, FeV₂L₂) and (H₃O)[Fe(bpy)₃]₄[V₃O₇(S-mand)₂]₃·28H₂O (2, FeV₃L₂) (bpy = 2,2’-bipyridine, mand^2– = mandelato ligand, C₈H₆O₃^2–) have been synthesized and characterized by single crystal X-ray diffraction and spectral methods. The FeSO₄—bpy—KVO₃—H₂mand—H₂O—CH₃CN system exhibits a stereospecific behaviour: while from the system including racemic mandelic acid only the complex of the V₂L₂ type (1) could be obtained in crystalline form, the system with S-mandelic acid afforded the V₃L₂ (2) complex as the single crystalline product. All vanadium atoms exhibit tetragonal pyramidal coordination geometry with oxygen donor atoms of the oxido ligands and carboxylate anion. The stereospecific behaviour was investigated using the ⁵¹ V NMR spectroscopy, which revealed different composition of systems with racemic mandelic acid and S-mandelic acid after some preliminary period (≈ 15 days). The compound 2 is chiral non-racemic compound (space group P2₁2₁2), the structure of which contains Δ-[Fe(bpy)₃]²⁺ cations and [V₃O₇(S-mand)₂]^3– anions.

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以[Fe(2,2 ' -联吡啶)3]2+为反离子的钒锰配合物的立体定向形成

合成了以[Fe(bpy)3]2+为对离子的扁桃酸钒配合物[Fe(bpy)3][V2O4(ac-mand)2]·4.9H2O·0.1CH3CN (1, FeV2L2)和(h30)[Fe(bpy)3]4[V3O7(S-mand)2]3·28H2O (2, FeV3L2) (bpy = 2,2 ' -联吡啶，mand2 - =扁桃酸配体，C8H6O32 -)，并用单晶x射线衍射和光谱方法对其进行了表征。feso4 - bby - kvo3 - h2mand - h2o - ch3cn体系表现出立体定向行为:从含有外消旋扁桃酸的体系中，只能得到V2L2(1)型配合物的结晶形式，而含有s -扁桃酸的体系则可以得到V3L2(2)型配合物的单晶产物。所有钒原子均与氧化配体的氧供体原子和羧酸阴离子呈四方锥体配位。用51 V核磁共振光谱对其立体定向行为进行了研究，结果表明外消旋扁桃酸和s -扁桃酸经过一段时间(≈15天)后形成了不同的体系。化合物2为手性非消旋化合物(空间基团P21212)，其结构中含有Δ-[Fe(bpy)3]2+阳离子和[V3O7(S-mand)2]3 -阴离子。图形抽象

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来源期刊

Transition Metal Chemistry 化学-无机化学与核化学

CiteScore

3.60

自引率

0.00%

发文量

审稿时长

1.3 months

期刊介绍： Transition Metal Chemistry is an international journal designed to deal with all aspects of the subject embodied in the title: the preparation of transition metal-based molecular compounds of all kinds (including complexes of the Group 12 elements), their structural, physical, kinetic, catalytic and biological properties, their use in chemical synthesis as well as their application in the widest context, their role in naturally occurring systems etc. Manuscripts submitted to the journal should be of broad appeal to the readership and for this reason, papers which are confined to more specialised studies such as the measurement of solution phase equilibria or thermal decomposition studies, or papers which include extensive material on f-block elements, or papers dealing with non-molecular materials, will not normally be considered for publication. Work describing new ligands or coordination geometries must provide sufficient evidence for the confident assignment of structural formulae; this will usually take the form of one or more X-ray crystal structures.