修飾掌性三氮配基金屬串錯合物之合成與結構研究

Abstract

本實驗室長年致力於多氮配基與金屬的配位化學上的研究，其中多核及混金屬的金屬串錯合物陸陸續續被發表出來。由於配基以螺旋的方式和金屬離子配位，在絕對構型上金屬串錯合物包含了Λ和Δ兩種光學異構物。本論文之研究目標在於結合傳統二吡啶胺配基與新開發的掌性三氮配基合成混配基線形三核金屬串錯合物，藉由掌性配基配位而去分離出兩種掌性金屬串錯合物 : Λ和Δ 構型。 本論文利用了掌性配基 ((-)H2dcamap) 和 ((+)H2dcamap) 與傳統三氮配基 Hdpa 成功合成出三個金屬串錯合物 : [Ni3(dpa)2((-)dcamap)2(H2O)]、[Ni3(dpa)2((+)dcamap)2] 與[Cu3(dpa)2((+)dcamap)2] 。由 X – ray 單經結構解析，三種錯合物其相同兩配基分別以對位的形式與金屬離子配位，屬於 (2,2-trans) 構型。同時發現在三個錯合物的單晶裡同時發現 Λ和Δ 構型。本論文在此針對三種錯合物的合成及結構去做進一步的探討。

We are interested in developing a new type of ligands which might bind oligonuclear metal ions. Here we synthesize ligands : ((2,6-(di-N-(-)-10-camphorsulfonyl)amido)pyridine)((-)H2dcamap) and ((2,6-(di-N-(+)-10-camphorsulfonyl)amido)pyridine)((+)H2dcamap) . We mix (2,2’-(dipyridyl)amine)(Hdpa) and ((-)H2dcamap) and ((+)H2dcamap) to synthesize a nickel(II) and copper(II) complex : [Ni3(dpa)2((-)dcamap)2(H2O)]、[Ni3(dpa)2((+)dcamap)2] and [Cu3(dpa)2((+)dcamap)2] . Because there are two different ligands in three metal strings. We may get two isomeric forms , (2,2)-cis or (2,2)-trans . By X-ray diffractions , (2,2)-trans of three metal strings has been characterized . Due to the torsion of ligands in metal strings , there two forms , Δ and Λ . When we synthesis metal strings , we get two forms of metal strings and can not only get Δ or Λ form . One of our goal is to isolated Δ and Λ forms , so we control the chirality of ligands and expect that we can control the chirality of metal strings . After X-ray diffraction , we discover that we still get two forms of metal strings of three metal strings .