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研究生:潘靜瑤
研究生(外文):Jing-Yao Pan
論文名稱:具光學活性雙胺配位基與金屬四重鍵化合物及含2-胺基啶配位基與鈀金屬之化合物合成、結構與光譜之研究
論文名稱(外文):Synthesis, Spectra and Structures of Quadruply Bonded Complexes Containing Chiral Diamine Ligands and Palladium Complexes Containing 2-Amino Pyridine Lignad.
指導教授:陳志德
指導教授(外文):Jhy-Der Chen
學位類別:碩士
校院名稱:中原大學
系所名稱:化學系
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:1999
畢業學年度:87
語文別:中文
論文頁數:78
中文關鍵詞:光學活性旋光性掌形化合物發色團單電子偶合機構三中心二電子鍵三中心四電子鍵
外文關鍵詞:optical activitychromophoreone-electron static coupling mechanism3 center-2 electron bond3 center-4 electron bond
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本論文分兩部分探討具光學活性雙胺配位基與金屬四重鍵化合物的化學及含Hampy(Hampy = 2-amino-6-methylpyridine)與Hapy(Hapy = 2-aminopyridine)配位基與鈀金屬化合物之結構。藉由起始物[Mo2(O2CCF3)2(CH3CN)6][BF4]2與含旋光性[(R,R-dach) = (1R,2R)-(-)-trans-cyclohexanediamine;(S,S-dach) = (1S,2S)-(+)-cis-cyclohexanediamine在CH3CN中反應,可以得到產物[Mo2(O2CCF3)2(S,S-dach)2][BF4]2,1,[Mo2(O2CCF3)2(R,R-dach)2][BF4]2,2。它們的UV-vis和CD光譜已有記錄,同時化合物1和2的結構也已被決定。化合物1的晶體資料:空間群為P2,a = 9.362(1) A,b = 9.622(1) A,c = 18.962(1) A,V = 1710(2) A3,Z = 2,R1 = 0.0348,wR2 = 0.0940。化合物2的晶體資料:P2,a = 9.361(1) A,b = 9.624(1) A,c = 18.977(1) A,V = 1710(2) A3,Z = 2,R1= 0.0513,wR2 = 0.1314。
另外,由起始物Mo2(O2CCH3)2Cl2(PPh3)2、Mo2(O2CCH3)2Br2(PPh3)2、Mo2(O2CCF3)2Cl2(PPh3)2、及Mo2(O2CCF3)2Br2 (PPh3)2,分別與(R,R-dach)與(S,S-dach)在THF中反應,可得到產物Mo2(O2CCH3)2Cl2(S,S-dach),3,Mo2(O2CCH3)2Cl2 (R,R-dach),4,Mo2(O2CCH3)2Br2(S,S-dach),5,Mo2(O2C CH3)2Br2(R,R-dach),6,Mo2(O2CCF3)2Cl2(S,S-dach),7,Mo2 (O2CCF3)2Cl2(R,R-dach),8,Mo2(O2CCF3)2Br2(S,S-dach),9,Mo2(O2CCF3)2Br2(R,R-dach),10,。它們的UV-vis光譜和CD光譜已有記錄。掌形化合物3及4、5及6、7及8、9及10的CD光譜是互為鏡像的關係。
PdCl2與二當量的Hampy (Hampy = 2-amino-6-methyl pyridine)及Hapy (Hapy = 2-aminopyridine)在CH3CN下反應形成PdCl2(Hampy)2,11及PdCl2(Hapy)2,12,而此化合物具有非線性的N-H…Pd(II)的作用。化合11已有晶體結構,空間群為Pca21,a = 8.0531(7) A,b = 14.061(1) A,c = 13.284(1) A,V = 1504.3(2) A3,Z = 4,R1 = 0.0521,wR2 = 0.1373。Pd原子配位二個氯原子及二個成trans構造的Hampy配位基,而Cl-Pd-Cl及N-Pd-N的角度為178.0(3)°及178.7(4)°。這個結構有趣的地方為Hampy配位基的胺基位置,很明顯的是胺基位在Pd中心原子的配位平面之上及之下,胺基的兩個氫原子被迫與Pd原子作用,造成兩個trans N-H…Pd(II)的作用力,化合物12之結構應與11相似。

This thesis includes two parts. The first part discusses the synthesis, structures and optical activities of quadruple-bonded complexes containing chiral diamine ligands. The second part discusses synthesis and structures of palladium complexes containing amino pyridine ligand.
The complexes [Mo2(O2CCF3)2(S,S-dach)2][BF4]2, 1, and [Mo2(O2CCF3)2(R,R-dach)2][BF4]2 , 2 , (dach = 1,2-diamino cyclohexane) were prepared by reactions of [Mo2(O2CCF3)2 (CH3CN)6[BF4]2 with (S,S-dach)and (R,R-dach), respectively, in CH3CN. Their UV-vis and circular dichroism(CD) spectra have been recorded the structures have been determined by X-ray crystallgraphy. Crystal data for 1: space group P2, a = 9.362(1) A, b = 9.622(1) A, c = 18.962(1) A, V = 1710(2) A3, Z = 2, with final residuals R1 = 0.0348, wR2 = 0.0940. Crystal data for 2: space group P2, a = 9.361(1) A, b = 9.624(1) A, c = 18.977(1) A, V = 1710(2) A3, Z = 2, with final residuals R1= 0.0513, wR2 = 0.1314. The metal centers are bridged by the two O2CCF3 groups which are cis to each other and chelated by two dach ligands. The absorption wavelength at 510 nm for both 1 and 2 can be assigned to dxy Rdxy* transitions. The solution CD spectra of these two complexes show two prominent bands at 510 and 405nm and form mirror images of each other. The one-electron static coupling mechanism was invoked to explain the CD spectrum for these complexes.
The reaction of Mo2(O2CCR3)2X2(PPh3)2 with one equivalent of (R,R-dach) or (S,S-dach) in THF afforded the complex Mo2(O2CCR3)2X2(S,S-dach) (R = H, X = Cl, 3; R = H, X = Br, 5; R = F, X = Cl, 7, R = F, X = Br, 9) and Mo2(O2CCR3)2X2(R,R-dach) (R = H, X = Cl, 4; R = H, X = Br, 6; R = F, X = Cl, 8, R = F, X = Br, 10) Their UV-vis and CD spectra have been recorded.
Reaction of PdCl2 with 2-amino-6-methylpyridine (Hampy)(Hampy = 2-amino-6-methylpyridine) and 2-amino pyridine(Hapy)(Hapy = 2-aminopyridine) afforded the title complexes PdCl2(Hampy)2, and PdCl2(Hapy)2, respectively, which show a pair of nonlinear N-H…Pd(II) interactions. Crystal data for 11: space group Pca21, a = 8.0531(7) A, b = 14.061(1) A, c = 13.284(1) A, V = 1504.3(2) A3, Z = 4, with final residuals R1 = 0.0521, wR2 = 0.1373.

中文摘要………………………………………………………………Ⅰ
英文摘要………………………………………………………………Ⅲ
目錄……………………………………………………………………Ⅴ
表目錄…………………………………………………………………Ⅵ
圖目錄…………………………………………………………………Ⅷ
反應圖…………………………………………………………………1
前言……………………………………………………………………2
實驗部份………………………………………………………………8
X-ray 晶體結構解析…………………………………………………16
結果與討論
(一) 合成與結構探討…………………………………………………23
(二) 吸收光譜…………………………………………………………38
結論……………………………………………………………………53
參考文獻………………………………………………………………54
附錄……………………………………………………………………58

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