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研究生:梁修啟
研究生(外文):Shiu-Chi Liang
論文名稱:含多芽氮配位基與錸和銅金屬化合物之化學
論文名稱(外文):Chemistry of Rhenium and Copper Complexes Containing Polydentate Nitrogen Ligands
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:化學研究所
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:2002
畢業學年度:90
語文別:英文
論文頁數:101
中文關鍵詞:氫鍵有機無機混成材料錸及銅金屬
外文關鍵詞:Rhenium&Copperorganic-inorganic hybridHydrogen-bond
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本論文主要探討含多芽配位基與過渡金屬化合物的化學。
用化合物CuCl2·2H2O為起始物與配位基tpt (tpt = 2,4,6-tri(2-pyridyl)-1,3,5-triazine) 在HCl(aq) 下反應可得到化合物[tptH3][CuCl4]Cl,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P21/n,a = 10.3768(12) Å,b = 14.391(2) Å,c = 14.876(2) Å ,β= 97.989(11) □,V = 2200.0(5) Å3,Z = 4,R1 = 0.0741 and wR2 = 0.1429。用化合物CuBr2為起始在物與配位基tpt (tpt = 2,4,6-tri(2-pyridyl)-1,3,5-triazine) 在HBr(aq) 下反應可得到化合物[tptH3][CuBr4]Br,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的光譜已經被記錄下來,化合物2的空間群為P21/n,a = 10.7041(13) Å,b = 14.712(2) Å,c = 15.200(2) Å,β= 98.600(13) □,V = 2200.0(5) Å3,Z = 4,R1 = 0.0741 and wR2 = 0.1429。在化合物1與2中配位基tpt 以H3tpt3+ 陽離子的形式與金屬鹵化物MX42-陰離子,藉由分子間氫鍵形成。
用化合物ReBr(CO)5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ReBr(CO)3- (HDpyF),3 。化合物3的結構已經由單晶X-ray 繞射儀被測得,化合物3的光譜已經被記錄下來,化合物3的空間群為P21/c,a = 10.7610(13) Å,b = 9.065(2) Å,c = 16.189(2) Å,β= 91.523(8) □,V = 1578.7(4) Å3,Z = 4,R1 = 0.0567 and wR2 = 0.1373。用化合物ReBr(CO)5為起始在物與配位基HDMepyF (HDMepyF = N,N ′-di(6-methyl-2-pyridyl)formamidine 在THF 下反應可得到化合物ReBr(CO)3(HDMepyF),4 。化合物4的結構已經由單晶X-ray 繞射儀被測得,化合物4的光譜已經被記錄下來,化合物4的空間群為P ī,a = 7.044(2) Å,b = 10.170(3) Å,c = 16.189(2) Å,α= 83.07□,β= 82.54(3) □,γ= 77.35□,V = 917.8(5) Å3,Z = 2,R1 = 0.0540 and wR2 = 0.1297。在化合物3與4中配位基HDpyF 與HDMepyF 以分別以螯合的方式來與金屬部份鍵結。

This thesis discuss the chemistry of transition metal complexes containing polydentate ligands.
The complex [tptH3][CuCl4]Cl, 1, was prepared by reaction of CuCl2·2H2O with tpt (tpt = 2,4,6-tri(2-pyridyl)-1,3,5-triazine) in HCl(aq). The spectroscopic data of 1 has been recorded and the structure of 1 determined by X-ray crystallography. Crystal data for 1: space group P21/n, a = 10.3768(12) Å, b = 14.391(2) Å, c = 14.876(2) Å, β= 97.989(11) □, V = 2200.0(5) Å3, Z = 4, R1 = 0.0741 and wR2 = 0.1429. The complex [tptH3][CuBr4]Br, 2, was prepared by reaction of CuBr2 with tpt in HBr(aq). The spectroscopic data of 2 has been recorded and the structure of 2 determined by X-ray crystallography. Crystal data for 2: space group P21/n, a = 10.3768(12) Å, b = 14.391(2) Å, c = 14.876(2) Å, β= 97.989(11) □, V = 2200.0(5) Å3, Z = 4, R1 = 0.0741 and wR2 = 0.1429. The tptH3 cations in complexes 1 and 2 were interacted with anions through intermolecular hydrogen bonds.
The complex ReBr(CO)3(HDpyF), 3, was prepared by reaction of ReBr(CO)5 with HDpyF (HDpyF = N,N ′-di(2-pyridyl)formamidine) in THF. The spectroscopic data of 3 has been recorded and the structure of 3 determined by X-ray crystallography. Crystal data for 1: space group P21/c, a = 10.7610(13) Å, b = 9.065(2) Å, c = 16.189(2) Å, β= 91.523(8) □, V = 1578.7(4) Å3, Z = 4, R1 = 0.0567 and wR2 = 0.1373. The complex Re(CO)3Br(HDMepyF), 4, was prepared by reaction of ReBr(CO)5 with HDMepyF (HDMepyF = N,N ′-di(6-methyl-2-pyridyl)formamidine in THF. The spectroscopic data of 4 has been recorded and the structure of 4 determined by X-ray crystallography. Crystal data for 4: space group P ī, a = 7.044(2) Å, b = 10.170(3) Å, c = 16.189(2) Å, α= 83.07□, β= 82.54(3) □, γ= 77.35□, V = 917.8(5) Å3, Z = 2, R1 = 0.0540 and wR2 = 0.1297. The HDpyF and HDMepyF ligands in complexes 3 and 4 were coordinated to Re atoms in bidentate fashions and the Re metal centers form facial geometry with its ligands.

中文摘要 I
ABSTRACT III
INTRODUCTION 1
EXPERIMENTAL SECTION
General procedures 11
Instrument 11
Materials 11
Preparation of [tptH3][CuCl4]Cl 11
Preparation of [tptH3][CuBr4]Br 12
Preparation of Re(CO)3Br(HDpyF) 12
Preparation of ReBr(CO)3(HDMepyF) 13
X-ray Crystallography 14
RESULTS AND DISCUSSION
Structure of [tptH3][CuX4]X (X = Cl or Br) 18
Structure of ReBr(CO)3L (L = HDpyF or HDMepyF) 35
NMR of ReBr(CO)3L (L = HDpyF or HDMepyF) 46
CONCLUSION 56
REFERENCES 57
APPENDIX
Structure data61
Spectrum of NMR 81

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