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

作者：Chen, Xinjie; Chen, Ping; Zhang, Jie; Zhang, Shaowei; Yu, Xianyong^*; Li, Xiaofang^*

来源：Journal of Coordination Chemistry, 2018, 71(19): 3117-3126.

DOI：10.1080/00958972.2018.1512707

• Diperoxovanadium
• 2-hydroxymethyl pyridine derivatives
• steric effect
• NMR
• DFT-calculation

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(O-2)(2)(D2O)](-)/[OV(O-2)(2)(HOD)](-) in solution were explored by the combined use of multinuclear (H-1, C-13, and V-51) 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(O-2)(2)L](-) (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. @@@ [GRAPHICS] @@@ .

• 出版日期2018-10-2
• 单位湖南科技大学