论文部分内容阅读
为探讨单齿/双齿吡啶类配体对反应平衡的影响,在模拟生理条件下(0.15mol·L-1NaCl溶液),应用多核(1H、13C和51V)多维(COSY,HSQC和HMBC)以及变温NMR技术研究双过氧钒配合物[OV(O2)2(D2O)]-/[OV(O2)2(HOD)]-(简写为bpV)与系列吡啶类配体的相互作用,研究结果表明bpV与有机配体的反应性从强到弱的顺序为:2,2′-联吡啶>2,2′-联吡啶-4,4′-二甲酸根>吡啶>异烟酸根,这说明双齿吡啶类配体配位能力强于单齿配体,而不带羧基的吡啶类配体(单齿或双齿)配位能力强于所对应的带羧基的取代吡啶,竞争配位导致一系列新的6配位(配体为吡啶或异烟酸根)或7配位(配体为2,2′-联吡啶或2,2′-联吡啶-4,4′-二甲酸根)的过氧钒物种[OV(O2)2LL′]n-(LL′=吡啶类配体,n=1,2,3)生成。
In order to investigate the effect of monodentate / bidentate pyridine ligands on the reaction equilibrium, multicomponent (1H, 13C and 51V) multidimensional (COZY, HSQC and HMBC) were applied under simulated physiological conditions (0.15 mol·L-1 NaCl solution) Study on the Interaction of Divalent Vanadium Complex [OV (O2) 2 (D2O)] - / [OV (O2) 2 (HOD)] - (abbreviated as bpV) The order of the reactivity of bpV to organic ligands from strong to weak is: 2,2’-dipyridyl> 2,2’-bipyridine-4,4’-dicarboxylate> pyridine> isonicotinate, which means that Bidentate pyridine ligands have stronger coordination ability than monodentate ligands, while the ligands without carboxyl groups (monodentate or bidentate) have stronger coordination ability than the corresponding substituted pyridine with carboxyl groups. The competitive coordination results in A series of new 6-coordinate ligands (pyridine or isonicotinate) or 7-coordinate (with 2,2’-dipyridyl or 2,2’-bipyridyl-4,4’-dicarboxylate ligand) Of the vanadyl species [OV (O2) 2LL ’] n- (LL’ = pyridine ligands, n = 1, 2, 3).