Peter Schwendt, Róbert Gyepes, Jozef Tatiersky, Juraj Filo, Marek Bujdoš, Dominika Zákutná, Lukáš Krivosudský
{"title":"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","authors":"Peter Schwendt, Róbert Gyepes, Jozef Tatiersky, Juraj Filo, Marek Bujdoš, Dominika Zákutná, Lukáš Krivosudský","doi":"10.1007/s11243-023-00543-w","DOIUrl":null,"url":null,"abstract":"<div><p>Two vanadium complexes of mandelic acid having [Fe(<i>bpy</i>)<sub>3</sub>]<sup>2+</sup> as counterion, [Fe(<i>bpy</i>)<sub>3</sub>][V<sub>2</sub>O<sub>4</sub>(<i>rac</i>-<i>mand</i>)<sub>2</sub>]·4.9H<sub>2</sub>O·0.1CH<sub>3</sub>CN (<b>1</b>, FeV<sub>2</sub>L<sub>2</sub>) and (H<sub>3</sub>O)[Fe(<i>bpy</i>)<sub>3</sub>]<sub>4</sub>[V<sub>3</sub>O<sub>7</sub>(<i>S</i>-<i>mand</i>)<sub>2</sub>]<sub>3</sub>·28H<sub>2</sub>O (<b>2</b>, FeV<sub>3</sub>L<sub>2</sub>) (<i>bpy</i> = 2,2’-bipyridine, <i>mand</i><sup>2–</sup> = mandelato ligand, C<sub>8</sub>H<sub>6</sub>O<sub>3</sub><sup>2–</sup>) have been synthesized and characterized by single crystal X-ray diffraction and spectral methods. The FeSO<sub>4</sub>—<i>bpy</i>—KVO<sub>3</sub>—H<sub>2</sub><i>mand</i>—H<sub>2</sub>O—CH<sub>3</sub>CN system exhibits a stereospecific behaviour: while from the system including racemic mandelic acid only the complex of the V<sub>2</sub>L<sub>2</sub> type (<b>1</b>) could be obtained in crystalline form, the system with <i>S</i>-mandelic acid afforded the V<sub>3</sub>L<sub>2</sub> (<b>2</b>) 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 <sup>51</sup> V NMR spectroscopy, which revealed different composition of systems with racemic mandelic acid and <i>S</i>-mandelic acid after some preliminary period (≈ 15 days). The compound <b>2</b> is chiral non-racemic compound (space group <i>P</i>2<sub>1</sub>2<sub>1</sub>2), the structure of which contains Δ-[Fe(<i>bpy</i>)<sub>3</sub>]<sup>2+</sup> cations and [V<sub>3</sub>O<sub>7</sub>(<i>S</i>-<i>mand</i>)<sub>2</sub>]<sup>3–</sup> anions.</p><h3>Graphical abstract</h3>\n <figure><div><div><div><picture><source><img></source></picture></div></div></div></figure>\n </div>","PeriodicalId":803,"journal":{"name":"Transition Metal Chemistry","volume":"48 5","pages":"297 - 305"},"PeriodicalIF":1.6000,"publicationDate":"2023-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s11243-023-00543-w.pdf","citationCount":"0","resultStr":"{\"title\":\"Stereospecific formation of vanadium mandelato complexes with [Fe(2,2′-bipyridine)3]2+ as a counter ion\",\"authors\":\"Peter Schwendt, Róbert Gyepes, Jozef Tatiersky, Juraj Filo, Marek Bujdoš, Dominika Zákutná, Lukáš Krivosudský\",\"doi\":\"10.1007/s11243-023-00543-w\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Two vanadium complexes of mandelic acid having [Fe(<i>bpy</i>)<sub>3</sub>]<sup>2+</sup> as counterion, [Fe(<i>bpy</i>)<sub>3</sub>][V<sub>2</sub>O<sub>4</sub>(<i>rac</i>-<i>mand</i>)<sub>2</sub>]·4.9H<sub>2</sub>O·0.1CH<sub>3</sub>CN (<b>1</b>, FeV<sub>2</sub>L<sub>2</sub>) and (H<sub>3</sub>O)[Fe(<i>bpy</i>)<sub>3</sub>]<sub>4</sub>[V<sub>3</sub>O<sub>7</sub>(<i>S</i>-<i>mand</i>)<sub>2</sub>]<sub>3</sub>·28H<sub>2</sub>O (<b>2</b>, FeV<sub>3</sub>L<sub>2</sub>) (<i>bpy</i> = 2,2’-bipyridine, <i>mand</i><sup>2–</sup> = mandelato ligand, C<sub>8</sub>H<sub>6</sub>O<sub>3</sub><sup>2–</sup>) have been synthesized and characterized by single crystal X-ray diffraction and spectral methods. The FeSO<sub>4</sub>—<i>bpy</i>—KVO<sub>3</sub>—H<sub>2</sub><i>mand</i>—H<sub>2</sub>O—CH<sub>3</sub>CN system exhibits a stereospecific behaviour: while from the system including racemic mandelic acid only the complex of the V<sub>2</sub>L<sub>2</sub> type (<b>1</b>) could be obtained in crystalline form, the system with <i>S</i>-mandelic acid afforded the V<sub>3</sub>L<sub>2</sub> (<b>2</b>) 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 <sup>51</sup> V NMR spectroscopy, which revealed different composition of systems with racemic mandelic acid and <i>S</i>-mandelic acid after some preliminary period (≈ 15 days). The compound <b>2</b> is chiral non-racemic compound (space group <i>P</i>2<sub>1</sub>2<sub>1</sub>2), the structure of which contains Δ-[Fe(<i>bpy</i>)<sub>3</sub>]<sup>2+</sup> cations and [V<sub>3</sub>O<sub>7</sub>(<i>S</i>-<i>mand</i>)<sub>2</sub>]<sup>3–</sup> anions.</p><h3>Graphical abstract</h3>\\n <figure><div><div><div><picture><source><img></source></picture></div></div></div></figure>\\n </div>\",\"PeriodicalId\":803,\"journal\":{\"name\":\"Transition Metal Chemistry\",\"volume\":\"48 5\",\"pages\":\"297 - 305\"},\"PeriodicalIF\":1.6000,\"publicationDate\":\"2023-08-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://link.springer.com/content/pdf/10.1007/s11243-023-00543-w.pdf\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Transition Metal Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s11243-023-00543-w\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Transition Metal Chemistry","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s11243-023-00543-w","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Stereospecific formation of vanadium mandelato complexes with [Fe(2,2′-bipyridine)3]2+ as a counter ion
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, mand2– = mandelato ligand, C8H6O32–) 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.
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.
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