萃取法研究Cu^(2+)-dpx-PCA^-体系配体间的芳环堆积作用及其配合物的组成

STUDIES ON THE AROMATIC RING STACKING INTERACTION AND THE CHEMICAL COMPOSITION OF THE Cu(Ⅱ) dpx PCA - SYSTEM BY EXTRACTION METHOD

用萃取法测定Ｃｕ２＋ｄｐｘＰＣＡ体系中的堆积百分数，其中ｄｐｘ＝２，２′联吡啶胺（ｄｐａ），２，２′联吡啶甲烷（ｄｐｍ）和２，２′联吡啶酮（ｄｐｋ）；ＰＣＡ－＝苯甲酸根（Ｂｚ－），２苯乙酸根（ＰＡｃ－），３苯丙酸根（ＰＰｒ－）和４苯丁酸根（ＰＢｕ－）。结果表明：堆积百分数与羧酸根中亚甲基数有关，其顺序为Ｂｚ－＜ＰＡｃ－＜ＰＰｒ－＜ＰＢｕ，同时还与ｄｐｘ的结构有关，其顺序为ｄｐａ＜ｄｐｍ＜ｄｐｋ。这是堆积作用对配体的结构要求及存在π电子协作效应的缘故。

The percentage of the stacked isomers of mixed ligand complexes of the three types Cu 2+ dpx PCA -, where dpx=2,2′ dipyridylamine(dpa), 2,2′ dipyridylmethane(dpm) and 2,2′ dipyridylketone(dpk); PCA -=benzonate(Bz -), 2 phenylacetate(PAc -), 3 phenylpropionate(PPr -) and 4 phenylbutyrate(PBu -) have been determined by extraction method in aqueous chloroform medium The chemical composition of the extracted complexes determined by the qualification logarithm method is [Cu(dpx)(PCA) 2] According to the calculation of the percentage of the stacked isomers, it shows that on the same concentration of dpx or PCA - the orders of the stacking degree are: Cu(dpx)(Bz) 2<Cu(dpx)(PAc) 2<Cu(dpx)(PPr) 2<Cu(dpx)(PBu) 2 and Cu(dpa)(PCA) 2 <Cu(dpm)(PCA) 2<Cu(dpk)(PCA) 2