新型天門冬胺酸之二價銅離子錯合物的合成與鑑定

Abstract

本研究已合成三個過渡金屬錯合物：(1)[Cu(L-pasp)(H2O)]．4H2O；(2) [Cu(D-pasp)(H2O)]．4H2O及(3) [Co(L-pasp)2]．H2O ，其中pasp為吡啶甲基天門冬胺酸。利用元素分析、紅外線光譜、紫外光可見光光譜、電子順磁光譜、圓二色光譜及X-光結構解析等方法，完成二價銅錯合物的結構鑑定，並探討其鍵結性質。 三者皆已完成X-光單晶結構解析，晶體資料如下： (1) [Cu(L-pasp)(H2O)]．4H2O： 斜方晶系（Orthorhombic），空間群為P212121，其晶格常數為：a = 8.5157(3) Å，b = 10.8984(3) Å，c = 17.6615(6) Å，Z = 4，精算值為：R = 0.0522 ， wR2 = 0.1227。 (2) [Cu(D-pasp)(H2O)]．4H2O： 斜方晶系（Orthorhombic），空間群為P21212，其晶格常數為：a = 11.2411(3) Å，b = 16.5043(5) Å，c = 8.4442(3) Å，Z = 4，精算值為：R = 0.0661 ，and wR2 = 0.0968 (3) [Co(L-pasp)2]．H2O： 斜方晶系（Orthorhombic），空間群為P212121，其晶格常數為：a = 9.8288(15) Å，b = 14.928(2) Å，c = 15.628(2) Å，Z = 4，精算值為：R = 0.0570，and wR2 = 0.1438。 從[Cu(L-pasp)(H2O)]．4H2O和[Cu(D-pasp)(H2O)]．4H2O的晶體結構中發現，兩者分別形成具有左旋及右旋的螺旋配位高分子，pasp所具有的光學活性(L或D)決定配位高分子的旋光性。

Novel transition metal complexes of N-pyridylmethyl-(L)-aspartic acid (L-pasp) and N-pyridylmethyl-(D)-aspartic acid (D-pasp) have been synthesized and characterized by elemental analyses, UV-VIS, CD and EPR spectroscopic measurements. The crystal structures of [Cu(L-pasp)(H2O)]．4H2O 、[Cu(D-pasp)(H2O)]．4H2O and [Co(L-pasp)2]．2H2O have been determined by X-ray diffraction method. The crystal data of three complexes are listed below: (1) [Cu(L-pasp)(H2O)]．4H2O crystal in the orthorhombic, space group P212121 with a = 8.5157(3) Å, b = 10.8984(3) Å, c = 17.6615(6) Å, Z = 4, R = 0.0522, and wR2 = 0.1227. (2) [Cu(D-pasp)(H2O)]．4H2O crystal in the orthorhombic, space group P21212 with a = 11.2411(3) Å, b = 16.5043(5) Å, c = 8.4442(3) Å, Z = 4, R = 0.0661 and wR2 = 0.0968. (3) [Co(L-pasp)2]．2H2O crystal in the orthorhombic，space group P212121 with a = 9.8288(15) Å，b = 14.928(2) Å，c = 15.628(2) Å，Z = 4，R = 0.0570，and wR2 = 0.1438。 In the crystal structures of [Cu(L-pasp)(H2O)]．4H2O and [Cu(D-pasp)(H2O)]．4H2O, both complexes formed infinite left-handed or right-handed helical coordination polymers respectively. The helix direction is determined by the chirality of the ligand.