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NMR study on the coordination of diperoxovanadium(V) complexes with 2-hydroxymethyl pyridine derivatives

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To understand the substitution effects of 2-hydroxymethyl pyridine on the reaction equilibrium, the interactions between a series of 2-hydroxymethyl pyridine derivatives and diperoxovanadium(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 together with HSQC in 0.15 mol L−1 NaCl ionic medium for mimicking the physiological conditions. Some direct NMR data are given for the first time. The relative reactivity among the 2-hydroxymethyl pyridine ligands is 2-hydroxymethyl pyridine (1) > 2-methoxymethyl pyridine (2) > 2-ethoxymethyl pyridine (3) > 2-propoxymethyl pyridine (4). The competitive coordination results in the formation of a series of new seven-coordinate diperoxovanadium species [OV(O2)2L] (L = 1, 2, 3, and 4). The results of density functional calculations indicated that steric effects play an important role in these reactions, providing a reasonable explanation on the relative reactivity of the 2-hydroxymethyl pyridine derivative.
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Keywords: 2-hydroxymethyl pyridine derivatives; DFT-calculation; Diperoxovanadium; NMR; steric effect

Document Type: Research Article

Affiliations: Key Laboratory of Theoretical Organic Chemistry Functional Molecule, Ministry of Education, Provincial Key Laboratory of Controllable Preparation and Functional Application of Fine Polymers, National Demonstration Center for Experimental Chemical Engineering and Materials, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, China

Publication date: October 2, 2018

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