NMR and theoretical study on the linking properties of peroxovanadium(V) complexes with the 3-aminomethyl-pyridine derivatives |
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| Authors: | Wen Xia Jie Zhang Lei Yang |
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| Affiliation: | Key Laboratory of Theoretical Organic Chemistry Functional Molecule, Ministry of Education, National Demonstration Center for Experimental Chemical Engineering and Materials, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, China |
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| Abstract: | To understand the substitution effects of 3-aminomethyl-pyridine on the reaction equilibrium, the interactions between a series of 3-aminomethyl-pyridine derivatives and peroxovanadium(V) complex [OV(O2)2(D2O)]?/[OV(O2)2(HOD)]? in solution were explored by the combined use of multinuclear (1H, 13C, and 51V) magnetic resonance spectroscopy together with HSQC in 0.15 M NaCl ionic medium for mimicking the physiological conditions. Some direct NMR data are given for the first time. The relative reactivity among the 3-aminomethyl-pyridine derivative ligands are N-(pyridin-3-ylmethyl)acetamide (1) ≈ N-(pyridin-3-ylmethyl)propionamide (2) > N-(pyridin-3-ylmethyl)pivalamide (3) > t-butyl(pyridin-3-ylmethyl)carbamate (4). The competitive coordination results in the formation of a series of new six-coordinate peroxovanadium species [OV(O2)2L]? (L = 1–4). The results of density functional calculations indicated that the solvation effects play an important role in these reactions, providing a reasonable explanation on the relative reactivity of the 3-aminomethyl-pyridine derivatives. |
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| Keywords: | Diperoxovanadium 3-aminomethyl-pyridine derivatives solvation effect NMR DFT-calculation |
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