我們成功的合成一系列的釔和鑭系金屬搭配雙苯酚基磷配位基之錯合物: {[tBuOPO]La(BH4)(THF)2}2，[tBuOPO]Gd(BH4)(THF)2，[tBuOPO]Y(BH4)(THF)2，[tBuOPO]Er(BH4)(THF)2，[tBuOPO]Lu(BH4)(THF)2。並藉由X-ray單晶繞射和NMR光譜鑑定結構，將其應用在催化環己內酯來進行開環聚合反應。研究發現在不須外加起始劑的條件下，就能在室溫下反應，反應時間2.5到15分鐘且PDI介於1.11和1.24之間。實驗證明中心金屬對於催化活性有很大的影響。此外，聚合反應所得的高分子結構經氫譜比對證明為兩端皆為羥基(hydroxy group)的遙爪聚合物(telechelic polymer)。

A series of yttrium and lanthanide complexes containing a chelating biphenolate phosphine ligand were synthesized. These complexes are {[tBuOPO]La(BH4)(THF)2}2, [tBuOPO]Gd(BH4)(THF)2, [tBuOPO]Y(BH4)(THF)2, [tBuOPO]Er(BH4)(THF)2, [tBuOPO]Lu(BH4)(THF)2. Characterized by single-crystal X-ray diffraction, NMR spectroscopy and their application for the ring-opening polymerization of ε-caprolactone was studies. Research has concluded that the reaction without any additional initiator can be at room temperature, the reaction time is 2.5 to 15 minutes and the PDI is between 1.11 and 1.24. Experiments showed that the central metal has a great influence on the catalytic activity. In addition,polymer structure by NMR comparison proved to be the ends are all hydroxyl telechelic polymer.

論文審訂書 i
謝誌 ii
中文摘要 iii
Abstract iv
表目錄 viii
圖目錄 ix
一、緒論 1
1.1 雙苯酚磷化物 1
1.2 生物可降解材料 2
1.3 聚酯類介紹 2
1.3.1 聚己內酯(PCL) 2
1.3.2 聚乳酸(PLA) 4
1.4 聚合反應機制 7
1.5 稀土金屬化學 9
1.6 稀土硼氫化物 10
1.7 稀土硼氫錯合物 11
1.8 研究動機 25
二、結果與討論 26
2.1 配位基的合成 26
2.2 [tBuOPO]YCl合成與討論 26
2.3 [tBuOPO]YN(SiMe3)2合成與討論 35
2.4 [tBuOPO]H2與硼氫化釔的合成與討論 36
2.5 [tBuOPO]H2與硼氫化镥的合成與討論 41
2.6 [tBuOPO]H2與硼氫化鑭的合成與討論 43
2.7 [tBuOPO]H2與硼氫化稀土的合成與討論 45
2.8 以[tBuOPO]Y(BH4)(THF)2作為起始物的合成與討論 49
2.9 [tBuOPO]H2稀土硼氫化物ε-caprolactone開環聚合反應與探討 51
三、結論 54
四、實驗設計與合成 55
4.1 試劑 55
4.2 儀器設備 55
4.3 溶劑的純化 56
4.4 實驗步驟 57
4.4.1 2-bromo-4，6-di-tert-butylphenol的合成 57
4.4.2 [tBuOPO]H2配位基的合成 58
4.4.3 無水稀土氯化物的合成 59
4.4.4 Y[N(SiMe3)2]3的合成 59
4.4.5 稀土硼氫化物的合成 60
4.4.6 [tBuOPO]Y(BH4)(THF)2的合成 61
4.4.7 [tBuOPO]Lu(BH4)(THF)2的合成 62
4.4.8 {[tBuOPO]La(BH4)(THF)2}2的合成 63
4.4.9 [tBuOPO]Er(BH4)(THF)2的合成 64
4.4.10 [tBuOPO]Gd(BH4)(THF)2的合成 64
4.4.11 [tBuOPO]Ln(BH4)(THF)2的合成 65
4.4.12 [tBuOPO]Ti(OiPr)2的合成 65
4.4.13 [tBuOPO]YCl(DME)的合成的合成 66
4.4.14 [tBuOPO]YN(SiMe3)2(THF)的合成 66


4.5 官能基化己內酯的合成 67
4.5.1 Benzyl 4-hydroxycyclohexane carbamate的合成 67
4.5.2 Benzyl 4-oxocyclohexane carbamate的合成 67
4.5.3 γ-(Carbamic acid benzyl ester)-ε-caprolactone(CABCL)的合成 68
4.5.4 5-ethylene ketal ε-caprolactone(TOSUO)的合成 68
4.6 N-carboxyanhydride和O-carboxyanhydride的合成 69
4.6.1 L-Alanine N-carboxyanhydride的合成 69
4.6.2 γ-Benzyl-L-glutamate N-carboxyanhydride的合成 70
4.6.3 L-lac O-carboxyanhydride的合成 70
五、參考文獻 71
六、附錄 76
6.1 官能基化ε-caprolactone的開環聚合反應 76
6.2 晶體資料 80
6.3 Crystallographic data 87

(1) Fryzuk, M. D.; MacNeil, P. A.; Rettig, S. J.; Secco, A. S.; Trotter, J. Organometallics 1982, 1, 918.
(2) Fryzuk, M. D.; Haddad, T. S.; Rettig, S. J. Organometallics 1992, 11, 2967.
(3) Fryzuk, M. D.; Leznoff, D. B.; Ma, E. S. F.; Rettig, S. J.; Young, V. G. Organometallics 1998, 17, 2313.
(4) Lee, J.-H.; Pink, M.; Caulton, K. G. Organometallics 2006, 25, 802.
(5) Liang, L.-C.; Lin, J.-M.; Hung, C.-H. Organometallics 2003, 22, 3007.
(6) Fan, L.; Foxman, B. M.; Ozerov, O. V. Organometallics 2004, 23, 326.
(7) Harkins, S. B.; Peters, J. C. J. Am. Chem. Soc. 2005, 127, 2030.
(8) Bailey, B. C.; Huffman, J. C.; Mindiola, D. J.; Weng, W.; Ozerov, O. V. Organometallics 2005, 24, 1390.
(9) Liang, L.-C.; Chang, Y.-N.; Lee, H. M. Inorg. Chem. 2007, 46, 2666.
(10) Liang, L.-C.; Cheng, L.-C.; Tsai, T.-L.; Hu, C.-H.; Guo, W.-H. Inorg. Chem. 2009, 48, 5697.
(11) Liang, L.-C.; Hung, Y.-T.; Huang, Y.-L.; Chien, P.-S.; Lee, P.-Y.; Chen, W.-C. Organometallics 2011, 31, 700.
(12) Arbaoui, A.; Redshaw, C. Polym. Chem. 2010, 1, 801.
(13) Wang, J.-C.; Liu, Q.-K.; Ma, J.-P.; Huang, F.; Dong, Y.-B. Inorg. Chem. 2014.
(14) Leja, K.; Lewandowicz, G. Pol J Environ Stud 2010, 19, 255.
(15) Athanasiou, K. A.; Niederauer, G. G.; Agrawal, C. M. Biomaterials 1996, 17, 93.
(16) Sudesh, K.; Abe, H.; Doi, Y. Prog. Polym. Sci. 2000, 25, 1503.
(17) Labet, M.; Thielemans, W. Chem. Soc. Rev. 2009, 38, 3484.
(18) Martin, O.; Avérous, L. Polymer 2001, 42, 6209.
(19) Wang, X.-L.; Zhuo, R.-X.; Liu, L.-J.; He, F.; Liu, G. J. Polym. Sci., Part A: Polym. Chem. 2002, 40, 70.
(20) Gross, S. M.; Flowers, D.; Roberts, G.; Kiserow, D. J.; DeSimone, J. M. Macromolecules 1999, 32, 3167.
(21) Kohn, J.; Langer, R. J. Am. Chem. Soc. 1987, 109, 817.
(22) Anderson, J. M.; Gibbons, D. F.; Martin, R. L.; Hiltner, A.; Woods, R. J. Biomed. Mater. Res. 1974, 8, 197.
(23) French, A. C.; Thompson, A. L.; Davis, B. G. Angew. Chem. Int. Ed. 2009, 48, 1248.
(24) Wang, S.; Cai, Q.; Bei, J. Macromol. Symp. 2003, 195, 263.
(25) Woodruff, M. A.; Hutmacher, D. W. Prog. Polym. Sci. 2010, 35, 1217.
(26) Cheung, Y. W.; Stein, R. S. Macromolecules 1994, 27, 2512.
(27) Nair, L. S.; Laurencin, C. T. Prog. Polym. Sci. 2007, 32, 762.
(28) Platel, R. H.; Hodgson, L. M.; Williams, C. K. Polym. Rev. 2008, 48, 11.
(29) Hartmann, M. H. In Biopolymers from Renewable Resources; Kaplan, D., Ed.; Springer Berlin Heidelberg: 1998, p 367.
(30) Jacobsen, S.; Fritz, H. G.; Degée, P.; Dubois, P.; Jérôme, R. Polymer Engineering & Science 1999, 39, 1311.
(31) Xiao, L.; Wang, B.; Yang, G.; Gauthier, M. Biomedical Science, Engineering and Technology 2012, 11.
(32) Stanford, M. J.; Dove, A. P. Chem. Soc. Rev. 2010, 39, 486.
(33) Mecking, S. Angew. Chem. Int. Ed. 2004, 43, 1078.
(34) Zhou, X.; Zhao, X.; Wang, Y.; Wu, B.; Shen, J.; Li, L.; Li, Q. Inorg. Chem. 2014.
(35) Wilkinson, G.; Birmingham, J. M. J. Am. Chem. Soc. 1954, 76, 6210.
(36) Schumann, H. Angew. Chem. Int. Ed. Engl. 1984, 23, 474.
(37) Freeman, A. J.; Watson, R. E. Phys. Rev. 1962, 127, 2058.
(38) Beltrami, D.; Cote, G.; Mokhtari, H.; Courtaud, B.; Moyer, B. A.; Chagnes, A. Chem. Rev. 2014.
(39) Edelmann, F. T. Chem. Soc. Rev. 2009, 38, 2253.
(40) Marks, T. J.; Grynkewich, G. W. Inorg. Chem. 1976, 15, 1302.
(41) Ephritikhine, M. Chem. Rev. 1997, 97, 2193.
(42) Cendrowski-Guillaume, S. M.; Le Gland, G.; Nierlich, M.; Ephritikhine, M. Organometallics 2000, 19, 5654.
(43) Visseaux, M.; Terrier, M.; Mortreux, A.; Roussel, P. Comptes Rendus Chimie 2007, 10, 1195.
(44) Mahrova, T. V.; Fukin, G. K.; Cherkasov, A. V.; Trifonov, A. A.; Ajellal, N.; Carpentier, J.-F. Inorg. Chem. 2009, 48, 4258.
(45) Barbier-Baudry, D.; Blacque, O.; Hafid, A.; Nyassi, A.; Sitzmann, H.; Visseaux, M. Eur. J. Inorg. Chem. 2000, 2000, 2333.
(46) Bonnet, F.; Da Costa Violante, C.; Roussel, P.; Mortreux, A.; Visseaux, M. Chem. Commun. 2009, 3380.
(47) Zange, E. Chem. Ber. 1960, 93, 652.
(48) Mirsaidov, U.; Rotenberg, T. G.; Dymova, T. N. Dokl. Akad. Nauk Tadzh. SSR 1976, 19, 30.
(49) Mirsaidov, U.; Kurbonbekov, A.; Khikmatov, M. Zh. Neorg. Khim. 1982, 27, 2436.
(50) Mirsaidov, U.; Kurbonbekov, A. Dokl. Akad. Nauk Tadzh. SSR 1985, 28, 219.
(51) Mirsaidov, U.; Boiko, G. N.; Kurbonbekov, A.; Rakhimova, A. Dokl. Akad. Nauk Tadzh. SSR 1986, 29, 608.
(52) Cendrowski-Guillaume, S. M.; Nierlich, M.; Lance, M.; Ephritikhine, M. Organometallics 1998, 17, 786.
(53) Guillaume, S. M.; Schappacher, M.; Soum, A. Macromolecules 2002, 36, 54.
(54) Bonnet, F.; Visseaux, M.; Pereira, A.; Bouyer, F.; Barbier-Baudry, D. Macromol. Rapid Commun. 2004, 25, 873.
(55) Palard, I.; Soum, A.; Guillaume, S. M. Macromolecules 2005, 38, 6888.
(56) Yuan, F.; Zhu, Y.; Xiong, L. J. Organomet. Chem. 2006, 691, 3377.
(57) Shen, Q.; Yao, Y. J. Organomet. Chem. 2002, 647, 180.
(58) Skvortsov, G. G.; Yakovenko, M. V.; Castro, P. M.; Fukin, G. K.; Cherkasov, A. V.; Carpentier, J.-F.; Trifonov, A. A. Eur. J. Inorg. Chem. 2007, 2007, 3260.
(59) Jaroschik, F.; Bonnet, F.; Le Goff, X.-F.; Ricard, L.; Nief, F.; Visseaux, M. Dalton Trans. 2010, 39, 6761.
(60) Momin, A.; Bonnet, F.; Visseaux, M.; Maron, L.; Takats, J.; Ferguson, M. J.; Le Goff, X.-F.; Nief, F. Chem. Commun. 2011, 47, 12203.
(61) Dyer, H. E.; Huijser, S.; Susperregui, N.; Bonnet, F.; Schwarz, A. D.; Duchateau, R.; Maron, L.; Mountford, P. Organometallics 2010, 29, 3602.
(62) Barros, N.; Mountford, P.; Guillaume, S. M.; Maron, L. Chem. Eur. J. 2008, 14, 5507.
(63) Liang, L.-C.; Hsu, Y.-L.; Lin, S.-T. Inorg. Chem. 2011, 50, 3363.
(64) Fryzuk, M. D.; Haddad, T. S. J. Am. Chem. Soc. 1988, 110, 8263.
(65) Grunova, E.; Kirillov, E.; Roisnel, T.; Carpentier, J.-F. Dalton Trans. 2010, 39, 6739.
(66) O, W. W. N.; Kang, X.; Luo, Y.; Hou, Z. Organometallics 2014, 33, 1030.
(67) Schmid, M.; Guillaume, S. M.; Roesky, P. W. Organometallics 2014, 33, 5392.
(68) Zhang, L.; Suzuki, T.; Luo, Y.; Nishiura, M.; Hou, Z. Angew. Chem. 2007, 119, 1941.
(69) Cox, D. E.; Fong, F. K. J. Cryst. Growth 1973, 20, 233.
(70) Taylor, M. D. Chem. Rev. 1962, 62, 503.
(71) Bradley, D. C.; Ghotra, J. S.; Hart, F. A. J. Chem. Soc., Dalton Trans. 1973, 1021.
(72) Wu, G.; Sun, W.; Shen, Z. React. Funct. Polym. 2008, 68, 822.
(73) Yan, J.; Zhang, Y.; Xiao, Y.; Zhang, Y.; Lang, M. React. Funct. Polym. 2010, 70, 400.
(74) Babasola, O. I.; Amsden, B. G. Biomacromolecules 2011, 12, 3423.
(75) Habraken, G. J. M.; Peeters, M.; Dietz, C. H. J. T.; Koning, C. E.; Heise, A. Polymer Chemistry 2010, 1, 514.
(76) Markland, P.; Amidon, G. L.; Yang, V. C. Int. J. Pharm. 1999, 178, 183.
(77) Jérôme, C.; Lecomte, P. Adv. Drug Deliv.Rev. 2008, 60, 1056.