کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
1306923 | 975109 | 2010 | 6 صفحه PDF | دانلود رایگان |
![عکس صفحه اول مقاله: Effect of metal coordination and intra-molecular H-bond on the acidity of phenolic proton in a set of structurally characterized octahedral Ni(II) complexes of l-histidine derivative Effect of metal coordination and intra-molecular H-bond on the acidity of phenolic proton in a set of structurally characterized octahedral Ni(II) complexes of l-histidine derivative](/preview/png/1306923.png)
Four different mononuclear octahedral Ni(II) complexes with protonated and deprotonated form of the same ligand have been synthesized by controlling reaction conditions and structurally characterized. The complexes are [Ni(HLl-his)(benzoate)(MeOH)] (1), [Ni(HLl-his)(SCN)(MeOH)] (2), [Ni(HLl-his)2] (3) and [Ni(Ll-his)(imidazole)2] (4) where H2Ll-his is (S)-2-(2-hydroxybenzylamino)-3-(1H-imidazol-4-yl)-propionic acid. The ligand behaves as a monobasic tetradentate ligand in 1 and 2, monobasic tridentate ligand in 3 and dibasic tetradentate ligand in 4. Ni(II) coordinated phenolic proton of the ligand in the complexes 1–2 shows strong intra-molecular H-bonding with benzoate in 1 and lattice water in 2, whereas 3 shows intermolecular H-bonding between uncoordinated phenols with neighbouring carboxylate. The pH titration of the complexes revealed that metal coordination and H-bond in complexes 1 and 2 considerably lowers the acidity of ligand phenol (pKa 6.8 and 7.0 respectively) compared to phenol (pKa 10). The complex 4 does not show any proton loss due to the absence of phenolic proton. All the complexes show extensive H-bonded network in the crystals including narrow (7.8 × 5.2 Å) water filled one dimensional channel in 2.
pH titration was used to determine lowering of pKa of metal bound phenol as a result of metal coordination as well as due to strong intra-molecular H-bonding in a set of Ni(II) complexes.Figure optionsDownload as PowerPoint slide
Journal: Inorganica Chimica Acta - Volume 363, Issue 12, 15 October 2010, Pages 3055–3060