中文摘要
　　使用雙牙2-di-methylaminomethyl pyrrole （以下簡稱DMAMPH）及2-t-butylaminomethyl pyrrole （以下簡稱TBAMPH）吡咯衍生物配位基，和不對稱三牙吡咯衍生物配位基[C4H2NH(2-CH2NHtBu)(5-CH2NMe2)]與鎂金屬反應，獲得一系列鎂金屬錯化合物之合成與鑑定。
取DMAMPH與一當量的正丁基鋰於正庚烷下反應，利用吡啶再結晶生成(DMAMPLi)2Py2 (1)；取兩當量的DMAMPLi與一當量的碘化鎂或溴化鎂在四氫呋喃下反應，合成Mg(DMAMP)2(THF)2 (2)；取兩當量的TBAMPH與二正丁基鎂於四氫呋喃下反應，合成Mg(TBAMP)2(THF)2 (3)；取一當量的TBAMPH與二正丁基鎂於低溫四氫呋喃下反應，合成[Mg(TBAMP)(THF)]2 (4)；取TBAMPH與一當量的正丁基鋰於正庚烷下反應，利用吡啶再結晶生成(TBAMPLi)2Py2 (5)；取一當量的TBAMPLi與兩倍量CH3MgCl於四氫呋喃下反應，合成[Mg3(μ2-Cl)3(μ3-OMe)2(THF)6]2[{C4H2N(2-CH2NHtBu)MgCl}2] (6)；取兩當量 [C4H2NH(2-CH2NHtBu)(5-CH2NMe2)]與二正丁基鎂於甲苯下反應，合成{Mg[C4H2N(2-CH2NHtBu)(5-CH2NMe2)]}2 (7)；取一當量[C4H2NH(2-CH2NHtBu)(5-CH2NMe2)]與Mg[N(SiMe3)2]2於甲苯下反應，合成{[C4H2N(2-CH2NHtBu)(5-CH2NMe2)]MgN(SiMe3)2}2 (8)。
使用HOCMeCHCMeNAr（Ar = 2,6-iPr2C6H3）及HOCMeCHCMeNAr (Ar = 2-methoxypheny)酮胺衍生物配位基與鎂金屬反應，獲得一系列鎂金屬錯化合物之合成與鑑定。
取兩當量HOCMeCHCMeNAr與一當量的碘化鎂或溴化鎂於四氫呋喃反應，合成Mg(OCMeCHCMeNAr)2(THF) (9)；取兩當量HOCMeCHCMeNAr與二正丁基鎂於甲苯反應，合成Mg(OCMeCHCMeNAr)2 (10)；取一當量的碘化鎂和HOCMeCHCMeNAr與HOCMeCHCMeNAr於四氫呋喃反應，合成(OCMeCHCMeHNAr)2MgI2(THF)2 (11)與(HOCMeCHCMeNAr)2MgI2(THF)2 (12)。
所有合成之錯化合物皆經由氫和碳的核磁共振光譜儀加以鑑定，錯化合物1、2、3、4、5、6、8及9皆可經由再結晶純化，並且可得到適當晶體藉由X-ray單晶繞射儀加以鑑定。

Abstract
Employing bidentate dianionic pyrrole ligand, DMAMPH [2-dimethylaminomethyl pyrrole] and TBAMPH [2-tert-butylaminomethyl pyrrole], and asymmetrical tridentate dianionic pyrrolyl ligand, [C4H2N(2-CH2NHtBu)(5-CH2NMe2)] in combination with magnesium halides or alkyls under different conditions, several derivatives of magnesium have been generated and well characterized.
Reaction of one equiv. of n-BuLi with DMAMPH in heptane, and after recrystallization by pyridine, affords (DMAMPLi)2Py2 (1). Similarly, subjecting two equiv. of DMAMPLi with MgI2 or MgBr2 in tetrahydrofuran generates Mg(DMAMP)2(THF)2 (2). Also the reaction between two equiv. of TBAMPH and MgBu2 in tetrahydrofuran yields Mg(TBAMP)2(THF)2 (3). Reaction of one equiv. of TBAMPH with MgBu2 in tetrahydrofuran at low temperature affords [Mg(TBAMP)(THF)]2 (4). Again, reaction of one equiv. of n-BuLi with TBAMPH in haptane, and after recrystallization by pyridine produces (TBAMPLi)2Py2 (5). Furthermore, the reaction of one equiv. of TBAMPLi with two equiv. of CH3MgCl in tetrahydrofuran generates [Mg3(μ2-Cl)3(μ3-OMe)2(THF)6]2[{C4H2N(2-CH2NHtBu)MgCl}2] (6). Also, two new magnesium derivatives, {Mg[C4H2N(2-CH2NHtBu)(5-CH2NMe2)]}2 (7) and {[C4H2N(2-CH2NHtBu)(5-CH2NMe2)]MgN(SiMe3)2}2 (8), are originated by introducing [C4H2NH(2-CH2NHtBu)(5-CH2NMe2)] to either MgBu2 or Mg[N(SiMe3)2]2, respectively, in toluene.
Inserting bidentate keteminate lidand, HOCMeCHCMeNAr（Ar = 2,6-iPr2C6H3） and HOCMeCHCMeNAr (Ar = 2-methoxypheny) into magnesium reagents, several magnesium complexes have been synthesized and characterized.
Reaction of two equiv. of HOCMeCHCMeNAr with one equiv. of MgI2 or MgBr2 in tetrahydrofuran afford Mg(OCMeCHCMeNAr)2(THF) (9). Similarly, reaction of two equiv. of HOCMeCHCMeNAr with MgBu2 in toluene yields Mg(OCMeCHCMeNAr)2 (10). Also another two new compounds, (OCMeCHCMeHNAr)2MgI2(THF)2 (11) and (HOCMeCHCMeNAr)2MgI2(THF)2 (12), have been isolated by accumulation of one equiv. of MgI2 with HOCMeCHCMeNAr and HOCMeCHCMeNAr, respectively, in tetrahydrofuran.
All the aforementioned compounds are characterized by 1H and 13C NMR spectroscopy as well compounds 1, 2, 3, 4, 5, 6, 8 and 9 have been subjected to the X-ray diffraction technique in solid state.

中文摘要
英文摘要
第一章 緒論 1
第二章 結果與討論 9
第一節 含吡咯衍生物配位基之鎂金屬錯化合物的合成與鑑定 9
2-1-1 (DMAMPLi)2Py2 (1) 9
2-1-2 Mg(DMAMP)2(THF)2 (2) 11
2-1-3 Mg(TBAMP)2(THF)2 (3) 14
2-1-4 [Mg(TBAMP)(THF)]2 (4) 18
2-1-5 (TBAMPLi)2Py2 (5) 20
2-1-6 [Mg3(μ2-Cl)3(μ3-OMe)2(THF)6]2[{C4H2N(2-CH2NHtBu)MgCl}2] (6) 22
2-1-7 {Mg [C4H2N(2-CH2NHtBu)(5-CH2NMe2)]}2 (7) 28
2-1-8 {[C4H2N(2-CH2NHtBu)(5-CH2NMe2)]MgN(SiMe3)2}2 (8) 31
第二節 含酮胺衍生物配位基之鎂金屬錯化合物的合成與鑑定 36
2-2-1 Mg(OCMeCHCMeNAr)2(THF) （Ar = 2,6-iPr2C6H3）(9) 36
2-2-2 Mg(OCMeCHCMeNAr，)2 (Ar，= 2-methoxypheny) (10) 39
2-2-3 (OCMeCHCMeHNAr)2MgI2(THF)2 （Ar = 2,6-iPr2C6H3）(11) 40
2-2-4 (HOCMeCHCMeNAr，)2MgI2(THF)2 (Ar，=2-methoxypheny) (12) 41
第三章 結論 42
第四章 實驗部分 43
第一節 一般實驗 43
第二節 物理性質的測量 43
第三節 金屬錯化合物之合成 44
5-3-1 合成(DMAMPLi)2Py2 (1) 44
5-3-2 合成[Mg(DMAMP)2(THF)2 (2) 44
5-3-3 合成[Mg(TBAMP)2(THF)2 (3) 45
5-3-4 合成[Mg(TBAMP)(THF)]2 (4) 46
5-3-5 合成(TBAMPLi)2Py2 (5) 47
5-3-6 合成[Mg3(μ2-Cl)3(μ3-OMe)2(THF)6]2[{C4H2N(2-CH2NHtBu)MgCl}2] (6) 47
5-3-7 合成{Mg [C4H2N(2-CH2NHtBu)(5-CH2NMe2)]}2 (7) 48
5-3-8 合成{[C4H2N(2-CH2NHtBu)(5-CH2NMe2)]MgN(SiMe3)2}2 (8) 49
5-3-9 合成Mg(OCMeCHCMeNAr)2(THF)（Ar = 2,6-iPr2C6H3）(9) 50
5-3-10 合成Mg(OCMeCHCMeNAr，)2 (Ar，= 2-methoxypheny) (10) 50
5-3-11 合成(OCMeCHCMeHNAr)2MgI2(THF)2 （Ar = 2,6-iPr2C6H3）(11) 51
5-3-12 合成(HOCMeCHCMeNAr，)2MgI2(THF)2 (Ar，=2-methoxypheny) (12) 52
參考文獻 53
附錄 X-ray Data 55
圖次
圖 1-1 含生物可分解性聚合物的實際運用 2
圖2-1-1 The molecular structure of complex 1 10
圖2-1-2 1H- 13C HSQC 2D NMR spectrum of complex 2 in CDCl3 12
圖2-1-3 The molecular structure of complex 2 13
圖2-1-4 The molecular structure of complex 3 16
圖2-1-5 The molecular structure of complex 4 19
圖2-1-6 The molecular structure of complex 5 21
圖2-1-7 Variable-temperature NMR spectrum of complex 6 in d8-toluene 24
圖2-1-8 The anionic molecular structure of complex 6 25
圖2-1-9 The cationic molecular structure of complex 6 25
圖2-1-10 1H- 13C HSQC 2D NMR spectrum of complex 7 in C6D6 29
圖2-1-11 Homo-nuclear Decoupling NMR spectra of complex 7 in C6D6 30
圖2-1-12 Homo-nuclear Decoupling NMR spectra of complex 8 in C6D6 32
圖2-1-13 Variable-temperature NMR spectra of complex 8 in d8-toluene 33
圖2-1-14 The molecular structure of complex 8 34
圖2-2-1 The molecular structure of complex 9 38


表次
表 2-1-1 錯化合物1中心金屬周圍鍵長(Å)與鍵角(°) 10
表2-1-2 錯化合物2中心金屬周圍鍵長(Å)與鍵角(°) 13
表2-1-3 錯化合物3中心金屬周圍鍵長(Å)與鍵角(°) 16
表2-1-4 錯化合物2和3的選擇性鍵長及鍵角比較 17
表2-1-5 錯化合物4中心金屬周圍鍵長(Å)與鍵角(°) 19
表2-1-6 錯化合物5中心金屬周圍鍵長(Å)與鍵角(°) 21
表2-1-7 錯化合物6中心金屬周圍鍵長(Å)與鍵角(°) 26
表2-1-8 錯化合物8中心金屬周圍鍵長(Å)與鍵角(°) 35
表2-2-1 錯化合物9中心金屬周圍鍵長(Å)與鍵角(°) 38

式次
Scheme 1-1 Chisholm發表trispyrazolylborate配位基鎂、鈣金屬錯化合物的開環聚合反應機構 3
Scheme 1-2 Chisholm發表β-diketiminate配位基鎂金屬錯化合物 4
Scheme 1-3 Gibson發表β-diketiminate配位基合成二配位及三配位鎂金屬錯化合物 4
Scheme 1-4 ketimine配位基合成五配位鎂金屬錯化合物 5
Scheme 1-5 Lin發表EDBP-H2配位基合成四配位鎂錯化合物 6
Scheme 1-6 Lin發表ketimine配位基合成五配位鎂錯化合物 7
Scheme 1-7 開環聚合反應機構 7
Scheme 1-8 本篇論文所使用之配位基 8
Scheme 2-1-1 吡咯衍生物配位基之鋰鹽DMAMPLi (1)合成反應方程式 9
Scheme 2-1-2 錯化合物2之合成反應方程式 11
Scheme 2-1-3 錯化合物3、4之合成反應方程式 15
Scheme 2-1-4 吡咯衍生物配位基之鋰鹽TBAMPLi (5)合成反應方程式 20
Scheme 2-1-5 錯化合物6之合成反應方程式 22
Scheme 2-1-6 錯化合物6之陰離子反應機構 23
Scheme 2-1-7 錯化合物6之陽離子反應方程式 23
Scheme 2-1-8 錯化合物7之合成反應方程式 28
Scheme 2-1-9 錯化合物8之合成反應方程式 31
Scheme 2-1-10 錯化合物8在高溫及低溫之平衡反應式 34
Scheme 2-2-1 錯化合物9之合成反應方程式 37
Scheme 2-2-2 錯化合物10之合成反應方程式 40
Scheme 2-2-3 錯化合物11、12之合成反應方程式 41

參考文獻
(1) Albertsson, A. C.; Varma, I. K. Biomacromolecules 2003, 4, 1466.
(2) Cabaret, O. D.; Vaca, B. M.; Bourissou, D. Chem. Rev. 2004, 104, 6147.
(3) Mecking, S. Angew. Chem. Int. Ed. 2004, 43, 1078.
(4) Chisholm, M. H.; Gallucci, J. C.; Phomphrai, K. Inorg. Chem. 2004, 43, 6717.
(5) Chisholm, M. H.; Eilerts, N. W.; Huffman, J. C.; Iyer, S. S.; Pacold, M.; Phomphrai, K. J. Am. Chem. Soc. 2000, 122, 11845.
(6) Chisholm, M. H.; Gallucci, J. C.; Phomphrai, K. Inorg. Chem. 2005, 44, 8004.
(7) Gibson, V. C.; Segal, J. A.; White, A. J. P.; Williams, D. J. J. Am. Chem. Soc. 2000, 122, 7120.
(8) Huang, J. H.; Lee, W. Y.; Hsieh, H. H.; Hsieh, C. C.; Lee, H.M.; Lee, G. H.; Wu, T. C.; Chuang, S. H. Journal of Organometallic Chemistry 2007, 692, 1131.
(9) Shueh, M. L.; Wang, Y. S.; Huang, B. H.; Kuo, C. Y.; Lin, C. C. Macromolecules 2004, 37, 5155.
(10) Lin, C. C.; Tang, H. Y.; Chen, H. Y.; Huang, J. H. Macromolecules 2007, 40, 8855.
(11) Huang, W. C.; Lin, C. C. Inorg. Chem. 2009, 48, 728.
(12) Dubois, P.; Ropson, N.; Jerome, R.; Teyssie, P. Macromolecules 1996, 29, 1965.
(13) Yu, R. C.; Hung, C. H.; Huang, J. H.; Lee, H. Y.; Chen, J. T. Inorg. Chem. 2002, 41, 6450.
(14) Nomura, N.; Aoyama, T.; Ishii, R.; Kondo, T. Macromolecules 2005, 38, 5363.
(15) Ko, B. T.; Lin, C. C. J. Am. Chem. Soc. 2001, 123, 7973.
(16) O’Keefe, B. J.; Hillmyer, M. A.; Tolman, W. B. Dalton Trans. 2001, 2215.
(17) Wu, J. C.; Lin, C. C. Chem. Rev. 2006, 250, 602.
(18) Hormnirun, P.; Marshall, E. L.; Gibson, V. C.; White, A. J. P.; Williams, D. J. J. Am. Chem. Soc. 2004, 126, 2688.
(19) Kricheldorf, H. R. Makromol. Chem. 1993, 194, 1665.
(20) Chisholm, M. H.; Lin, C. C.; Galluccia, J. C.; Ko, B. T. Dalton Trans. 2003, 406.
(21) Chisholm, M. H.; Gallucci. J.; Phomphrai, K. Inorg. Chem. 2002, 41, 2785.
(22) Aubrecht, K. B.; Hillmyer, M. A.; Tolman, W. B. Macromolecules 2002, 35, 644.
(23) Nimitsiriwat, N.; Marshall, E. L.; Gibson, V. C.; Elsegood, M. R. J.; Dale, S. H. J. Am. Chem. Soc. 2004, 126, 13598.
(24) O’Keefe, B. J.；Breyfogle, L. E.；Hillmyer, M. A.；Tolman, W. B. J. Am. Chem. Soc. 2002, 124, 4384.
(25) Dove, A. P.; Gibson, V. C.; Marshall, E. L.; Rzepa, H. S.; White, A. J. P.; Willams, D. J. J. Am. Chem. Soc. 2006, 128, 9834.
(26) Chamberlain, B. M.; Cheng, M.; Moore, D. R.; Ovitt, T. M.; Lobkovsky, E. B.; Coates, G. F. J. Am. Chem. Soc. 2001, 123, 3229.
(27) Zhong, Z.; Dijkstra, P. J.; Christin, B.; Westerhausen, M.; Feijen J. Marcomolecules 2001, 34, 3863.
(28) Huang, J. H.; Chi, L. S.; Huang, F. M.; Kuo, P. C.; Zhou, C. C.; Lee, G. H.; Peng, S. M. Chinese Chemical Society, 2000, 47, 895.
(29) Chen, Y. C.; Lin, C. Y.; Li, C. Y.; Huang, J. H.; Chang, L. C.; Lee, T. Y. Chem. Eur. J. 2008, 14, 9747.
(30) Addison, A. W.; Rao, T. N.; Reedijk, J.; Rijn, J. V.; Verschoor, G. C. J. Chem. Soc., Dalton Trans. 1984, 1349.