VO(II)-π受体配合物的结构及其ESR波谱研究

本文考察了VOSO~4与a, a＇-联吡啶, 3,4,7,8-四甲基-1, 10-邻菲罗啉和1,10-邻菲罗啉在不同酸度(pH=1-14)的乙二醇-水(1:1)溶液中, 低温下的ESR波谱。发现当pH＜1.0时ˉA=118×10^-4T, 归属于VO(H2O)~5]^2+; 当pH＞11时ˉA=90×10^-4T, 归属于VO(OCH~2CH~2O)~2]^2-。1.0＜pH＜7之间VO(II)与三种配体分别生成四种或三种不同的配合物, 本文推测了它们的可能结构。利用测得的波谱参数, 计算了键参数和电子能级。发现键参数的值随溶液pH值增加而减少, 电子能级数据与实验结果吻合。利用电子光谱数据还计算了VO(phen)~2^2+的晶体场参数。

The studies on the structures and ESR spectra of oxovanadium complexes with π-acceptor ligands

The ESR spectra of oxovanadium complexes with a,a'-bipyridine, 3,4,7,8-tetramethyl-1,10-phenanthroline and 1,10-phenanthroline in glycol-water (1:1) solns. at various acidity(pH = 1-14) were observed at 77 K. When the pH is < 1.0, A = 118 ?10-4 T is attributed to the complex VO(H2O)5]2+; when pH > 11, A = 90 ?10-4T is attributed to the bidentate chelate of glycol VO(OCH2CH2O)2]2-.