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为探讨过氧钒配合物上有机配体对反应平衡的影响,在模拟生理条件下(0.15mol/LNaCl溶液)应用多核(1H,13C,和51V)多维(COSY和DOSY)NMR以及变温技术等谱学方法研究双过氧钒配合物[OV(O2)2L]n-{n=1～3,L=oxalate(缩写为oxa),picolinate(缩写为pic),bipyridine(缩写为bipy),和1,10-phenanthroline(缩写为phen),与它们配位的含钒物种分别缩写为bpV(oxa),bpV(pic),bpV(bipy)和bpV(phen)}与2-甲基咪唑(缩写为2-Me-Imi)的相互作用,实验结果表明2-Me-Imi与4种双过氧钒配合物的反应性从强到弱的顺序为:bpV(oxa)>bpV(pic)>bpV(bipy)>bpV(phen).研究表明金属中心上配体的配位能力和空间位阻都对反应平衡产生较大的影响关,键同词时:竞争配位的结果导致新的六配位的过氧物种[OV(O2)2(2-Me-Imi)]-的生成.
To investigate the effect of organic ligands on the reaction equilibrium of vanadate complexes, multicomponent (1H, 13C, and 51V) multidimensional (COZY and DOSY) NMR and temperature-changing techniques were applied under simulated physiological conditions (0.15mol / L NaCl solution) Spectroscopic methods were used to study the effects of diperoxo vanadium complexes [OV (O2) 2L] n- {n = 1-3, L = oxalate for oxa, picolinate for pic, bipyridine for bipy and 1, 10-phenanthroline (abbreviated as phen) and the vanadium-bearing species with which they are coordinated are abbreviated bpV (oxa), bpV (pic), bpV (bipy) and bpV (phen) 2-Me-Imi). The experimental results show that the reactivity of 2-Me-Imi and 4 kinds of diperoxo vanadium complexes from strong to weak: bpV (oxa)> bpV (bipy)> bpV (phen). The results show that coordination ability and steric hindrance of the ligand on the metal center all have a great impact on the reaction equilibrium. When the bond is the same, the competitive coordination results in a new six The generation of the peroxisome [OV (O2) 2 (2-Me-Imi)].