含多芽配位基及其過渡金屬化合物之研究

中文摘要本論文主要探討含多芽配位基與其金屬化合物的化學。用化合物W(CO)6為起始物與配位基HDpyF (HDpyF = N,N’-di(2-pyridyl)formamidine)在THF下反應可得到化合物W(CO)4(HDpyF)，1。化合物1的結構已經由單晶X-ray繞射儀被測得，化合物1的光譜已經被記錄下來。化合物1的空間群為Pī，a = 7.319(1) Å，b = 9.788(1) Å，c = 12.094(1) Å， = 79.901(1)º， = 79.243(1)º， = 69.497(1)º，V = 791.55(11) Å3，Z = 2，R = 0.0243 and Rw = 0.0648。利用化合物W(CO)6為起始物與另一新合成的配位基HDMpyF (HDMpyF = N,N’-di[2-(6-methyl-pyridyl)]formamidine)反應在Toluene下反應可得到化合物W(CO)4(HDMpyF)，2。化合物2的結構已經由單晶X-ray繞射儀被測得，化合物2的光譜也已經被記錄下來。化合物2的空間群為Pī，a = 7.184(1) Å，b = 10.132(2) Å，c = 13.276(2) Å， = 79.877(9)º， = 80.251(11)º， = 72.116(13)º，V = 898.5(2) Å3，Z = 2，R = 0.0489 and Rw = 0.1291。在化合物1與2中配位基HDpyF及HDMpyF分別以螯合的方式來與金屬原子鍵結。化合物1利用分子間氫鍵及芳香族{ stacking interaction形成一個巨大分子的結構，而化合物2僅利用芳香族{ stacking interaction形成一個巨大分子的結構。使用含嘧啶環的配位基dipm (dipm = dipyrimdylamine) 與金屬化合物Co(NO3)2·6H2O和Cu(NO3)2·6H2O於CH3OH下反應可分別得到Co(dipm)(NO3)2(CH3OH), 3與Cu(dipm)(NO3)2(CH3OH), 4，化合物3與4的結構已經由單晶X-ray繞射儀被測得，其光譜已經被記錄下來。化合物3的空間群為Pī，a = 6.959(1) Å，b = 7.353(1) Å，c = 14.667(1) Å， = 84.261(6)º， = 80.292(6)º， = 81.086(7)º，V = 728.69(10) Å3，Z = 2，R = 0.0248 and Rw = 0.0639。化合物4的空間群為Pī，a = 7.306 (1) Å，b = 7.373 (1) Å，c = 13.896(2) Å， = 95.225(8)º， = 94.396(9)º， = 98.998(9)º，V = 733.10(14) Å3，Z = 2，R = 0.0691 and Rw = 0.1602。在化合物3和4中配位基dipm以螯合的方式來與金屬原子鍵結，且化合物3和4均利用分子間氫鍵形成一個dimer的結構。利用化合物4-Amino-6-hydroxy-mecaptopyrimidine monohydrate與p-Tolnnenesulfonic Acid S-2-methylbutyl Ester和K2CO3在DMF下反應合成新的配位基S-6-Amino-2-(2-methylbutylsulfanyl)-pyrimidine-4-one (S-HAmbspo)，5。利用化合物4-Amino-6-hydroxy-mecaptopyrimidine monohydrate與p-Tolnnenesulfonic Acid methyl Ester和K2CO3在DMF下反應合成配位基6-Amino-2-methysulfanyl-3H-pyrimidine-4-one (HAmspo)，6。化合物5、6的結構已經由單晶X-ray繞射儀被測得，它們的光譜已經被記錄下來。化合物5的空間群為R3，a = b = 30.249(2) Å，c = 7.275(1) Å， = 120º，V = 5765.1(6) Å3，Z = 16，R = 0.0468 and Rw = 0.1234。化合物6的空間群為P21/n，a =11.059(2) Å，10.998(2) Å，11.775(2)Å， = 99.885(2)º，V = 1410.8 Å3，Z = 8，R = 0.0576 and Rw = 0.1188。化合物5和6都是利用分子間氫鍵及芳香族{ stacking interaction形成一個巨大分子的結構。利用配位基S-HAmbspo與金屬四重鍵起始物Mo2(OAc)4在THF下反應可得到化合物Mo2(S-Ambspo)4，7。化合物7的結構已經由單晶X-ray繞射儀被測得，它的光譜已被紀錄。另外利用化合物Cu(NO3)2·6H2O與S-HAmbspo在THF下反應可得到化合物Cu(S-HAmbspo)3(NO3)2，8。其結構已經由單晶X-ray繞射儀被測得，它的光譜也已經被紀錄。化合物7的空間群為I41，a = b = 15.6604(7) Å，c = 19.199(1) Å，V = 4708.5(4) Å3，Z = 4，R = 0.0493 and Rw = 0.1526。化合物8的空間群為P1，a = 8.560(1) Å，b = 16.055(1) Å，17.199(1) Å,， = 93.982(1)º， = 92.331(1)º， = 97.608(1)，V = 2334.0(2) Å3，Z = 2，R = 0.0766 and Rw = 0.2107。化合物7其配位基S-Ambspo以amino的氮原子及嘧啶環上的氮原子來與金屬鍵結，在本論文中將討論此配位基對雙鉬金屬化合物光學活性的影響來加以討論。化合物8亦是利用分子間氫鍵及芳香族{ stacking interaction形成一個巨大分子的結構。

關鍵字

氫鍵；晶體結構；過渡金屬；多芽配位基

並列摘要

ABSTRACT This thesis discusses the chemistry of transition metal complexes containing polydentate ligands. The complex W(CO)4(HDpyF), 1, was prepared by reaction of W(CO)6 with HDpyF (HDpyF = N,N’-di(2-pyridyl)formamidine) in THF. The spectroscopic data of 1 has been recorded and the structure of 1 determined by X-ray crystallography. Crystal data for 1: space group Pī, a = 7.319 (1) Å, b = 9.788(1) Å, c = 12.094 (1) Å, = 79.901(1)º, = 79.243(1)º, = 69.497(1)º, V = 791.55(11) Å3, and Z = 2, with final residuals R = 0.0243 and Rw = 0.0648. The complex W(CO)4(HDMPyF), 2, was prepared by reaction of W(CO)6 with HDMpyF (HDMpyF = N,N’-di[2-(6-methyl-pyridyl)]formamidine) in Toluene. The spectroscopic data of 2 has been recorded and the structure of 2 determined by X-ray crystallography. Crystal data for 2: space group Pī, a = 7.1840(9) Å, b = 10.132(2) Å, c = 13.276(2) Å, = 79.877(9)º, = 80.251(11)º, = 72.116(13)º, V = 898.5(2) Å3, and Z = 2, with final residuals R = 0.0489 and Rw = 0.1291. The HDPyF and HDMpyF ligands in complexes 1 and 2 were coordinated to the metal centers in novel bidentate fashions. Complexes 1 show supramolecular structure in the solid state by intermolecular hydrogen bonds and aromatic { stacking interactions. Complexes 2 shows supramolecular structure in the solid state through aromatic { stacking interactions. The complex Co(dipm)(NO3)2(CH3OH), 3, and Cu(dipm)(NO3)2(CH3OH), 4, were prepared by reaction of Co(NO3)2·6H2O and Cu(NO3)2·6H2O, respectively, with dipm (dipm = dipyridylamine) in CH3OH. The spectroscopic data of 3 and 4 have been recorded and the structure of 3 and 4 determined by X-ray crystallography. Crystal data of 3: space group Pī, a = 6.959(1) Å, b = 7.353(1) Å, c = 14.667(1) Å, = 84.261(6)º, = 80.292(6)º, = 81.086(7)º, V = 728.69(10) Å3, and Z = 2, with final residuals R = 0.0248 and Rw = 0.0639. Crystal data of 4: space group Pī，a = 7.306 (1) Å, b = 7.373 (1) Å, c = 13.896(2) Å, = 95.225(8)º, = 94.396(9)º, = 98.998(9)º, V = 733.10(14) Å3, and Z = 2, with final residuals R = 0.0691 and Rw = 0.1602。The dipm ligand in complexes 3 and 4 were coordinated to the metal centers in novel bidentate fashions. Complexes 3 and 4 show dimeric structure in the solid state through multiple N-H---N and C-H---N intermolecular hydrogen bonds. The new ligand S-6-Amino-2-(2-methylbutylsulfanyl)-pyrimidine-4-one (S-HAmbspo), 5, was prepared by reaction of 4-Amino-6-hydroxy-mecaptopyrimidine monohydrate with p-Tolnnenesulfonic Acid S-2-methylbutyl Ester and K2CO3 in DMF. The ligand 6-Amino-2-methysulfanyl-3H-pyrimidine-4-one (HAmspo), 6, was prepared by reaction of 4-Amino-6-hydroxy-mecaptopyrimidine monohydrate with p-Tolnnenesulfonic Acid methyl Ester and K2CO3 in DMF. Their spectroscopic data and Mass spectra have been recorded and their structures have been determined by X-ray crystallography. Crystal data for 5: space group R3, a = b = 30.249(2) Å, c = 7.275(1) Å, = 120º, V = 5765.1(6) Å3, and Z = 16, with final residuals R = 0.0468, and Rw = 0.1234. Crystal data for 6: space group P21/n, a =11.059(2) Å, 10.998(2) Å, 11.775(2)Å, = 99.885(2)º, V = 1410.8 Å3, and Z = 8, with final residuals R = 0.0576 and Rw = 0.1188. Complexes 5 and 6 show supramolecular structure in the solid state by intermolecular hydrogen bond and aromatic { stacking interactions. The quadruply bonded complex Mo2(S-Ambspo)4, 7, was prepared by reactions of Mo2(OAc)4 with S-HAmbspo in CH3CN. Its spectroscopic data have been recorded and the structure has been determined by X-ray crystallography. The complex Cu(S-HAmbspo)3(NO3)2, 8, was prepared by reactions of Cu(NO3)2·6H2O with S-HAmbspo in THF. Its spectroscopic data have been recorded and the structure has been determined by X-ray crystallography. Crystal data for 8: space group I4(1), a = 15.6604(7) Å, b = 15.6604(7) Å, c = 19.1990(12) Å, V = 4708.5(4) Å3, and Z = 4, with final residuals R = 0.0493 and Rw = 0.1526. Crystal data for 8: space group P1, a = 8.560(1) Å, b = 16.055(1) Å, 17.199(1) Å, = 93.982(1)º, = 92.331(1)º, = 97.608(1), V = 2334.0(2) Å3, and Z = 2, with final residuals R = 0.0766 and Rw = 0.2107. The S-Ambspo ligand coordinates to the metal centers through one amine nitrogen atom and one pyrimidine nitrogen atom. Its effect on the optical activity of the Mo24+ unit is discussed. Complex 8 also shows supramolecular structure in the solid state by intermolecular hydrogen bond and aromatic { stacking interactions.

並列關鍵字

crystal structure ； hydrogen bonds ； transition metal ； Polydentate Ligands

參考文獻

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國際替代計量

含多芽配位基及其過渡金屬化合物之研究

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