臺灣博碩士論文加值系統

設計合成一系列三牙希夫鹼及四牙吡唑啉酮配位基之銅、鎳及鋯金屬錯合物，其中銅與鎳錯合物顯示高催化活性於二氧化碳和環氧化物的共聚合反應，而鋯金屬錯合物則可有效地應用於乳酸交酯的開環聚合反應。

合成一系列三牙希夫鹼配位基的銅(1-11)與鎳(12-20)金屬錯合物，藉由紫外光/可見光光譜儀、紅外光光譜儀、元素分析儀及X光單晶繞射儀證實其結構。藉由調控不同官能基及合成條件，可合成單核、雙核及三核不同形式之結構。實驗結果顯示於二氧化碳和環氧化物的共聚合反應，雙核之銅錯合物之反應活性高於三核之銅錯合物。

相反地，在鎳金屬之中，三核活性略高於雙核錯核物。而鎳金屬錯合物活性高於銅金屬錯合物。利用質譜儀鑑定高分子的微結構可得知，利用鎳錯合物為催化劑所得高分子，是以醋酸根做為起始劑，進行一連串的聚合反應。

合成與鑑定一系列以四牙吡唑啉酮作為配位基的鋯金屬錯合物(21-28)，藉由核磁共振光譜儀，元素分析儀及X光單晶繞射儀證實其結構，固態結構顯示鋯化合物為一單核六配位結構。化合物21-28均顯示對左旋乳酸交酯的開環聚合反應具有良好的活性與控制性。實驗結果得知，支鏈上官能基對於鋯化合物之活性並無顯著之影響，但會影響聚乳酸交酯分子量的控制性。另外，改變配位基上的架橋官能基時，則對於分子量分布度有顯著的差異。

A series of copper, nickel and zirconium complexes bearing NNO-tridentate Schiff base or NNOO-tetradentate pyrazolonate ligands have been synthesized and characterized. Copper and nickel complexes are active catalysts in copolymerization of carbon dioxide with cyclohexene oxide, and zirconium complexes with NNOO-tetradentate pyrazolonate ligands effectively catalyze ring-opening polymerization of lactides.

Structurally diverse copper (1-11) and nickel (12-20) acetate complexes supported by NNO-tridentate Schiff-base ligands were synthesized and characterized as mono-, di-, and trinuclear complexes with respect to varied ancillary ligands. All complexes were obtained as air-stable crystalline solid and were characterized on the basis of mass, IR and ultraviolet-visible (UV-vis) spectra as well as elemental analysis.

Copper and nickel complexes are effective catalysts for copolymerization of cyclohexene (CHO) and CO2 and satisfactorily produce polycarbonates with controllable molecular weights and high carbonate linkages. The MALDI-TOF spectrum from the purified PCHC sample generated by tri-Ni 18 complex has been investigated to understand the microstructure and composition of the PCHC which is peculiar to a repeated unit of PCHC (142 Da) and the chain end was an OAc- group. This result suggests that the CO2/CHO copolymerization was initiated by the acetate group.

Eight tetradentate pyrazolonate zirconium complexes 21-28 have been prepared and characterized. These complexes have been employed as initiators for ring-opening polymerization of lactides, and reveal good activities in a controlled manner. Additionally, the different substituents at R1, R2 and the bridged diamine skelaton seem to exhibit the key factors for the ROP of L-LA to demonstrate well performance with low polydispersity index (PDI) of polymer and well-controlled molecular weight.

Chapter 1. Introduction 1
1.1 Introduction 1
1.2 CO2 Chemistry 3
1.3 Ring-opening Polymerization for Biodegradable Polymer 4
1.4 Historical Background 10
Chapter 2. Structurally Diverse Copper Complexes Bearing NNO-Tridentate Schiff-Base Derivatives as Efficient Catalysts for Copolymerization of Carbon Dioxide and Cyclohexene Oxide 26
2.1 Synthesis and Characterization for Copper Complexes 1-11 26
2.2 Crystal Structures of Copper Complexes 1-11 28
2.3 Copolymerization of CHO with CO2 with Copper Complexes 41
2.4 Summary 51
2.5 Experiment section 51
Chapter 3. Di- and Tri- Nickel Complexes as Effective Catalysts for Alternating Copolymerization on Carbon Dioxide and Cyclohexene Oxide 57
3.1 Synthesis and Characterization for Nickel Complexes 12-20. 57
3.2 Molecular Structures of Nickel Complexes 12–20. 61
3.3 Copolymerization of CHO with CO2 with Nickel Complexes 72
3.4 MALDI-TOF Mass Spectroscopic Studies 80
3.5 Summary 82
3.6 Experiment section 82
Chapter 4. Ring-Opening Polymerization of Lactide Catalyzed by Pyrazolonate Zirconium Complexes 87
4.1 Synthesis and Structural Characterization for Zirconium 87
4.2 Ring-Opening Polymerization of Lactides 90
4.3 Summary 93
4.4 Experiment section 93
Chapter 4. Conclusions 99
Chapter 5. Reference 100
Chapter 6. Appendix 107
6-1. X-ray Structural Data for complex 1 107
6-2. X-ray Structural Data for complex 2 124
6-3. X-ray Structural Data for complex 3 135
6-4. X-ray Structural Data for complex 4 153
6-5. X-ray Structural Data for complex 5 165
6-6. X-ray Structural Data for complex 6 177
6-7. X-ray Structural Data for complex 7 189
6-8. X-ray Structural Data for complex 8 201
6-9. X-ray Structural Data for complex 9 213
6-10. X-ray Structural Data for complex 10 231
6-11. X-ray Structural Data for complex 11 242
6-12. X-ray Structural Data for complex 12 254
6-13. X-ray Structural Data for complex 13 274
6-14. X-ray Structural Data for complex 14 291
6-15. X-ray Structural Data for complex 15 310
6-16. X-ray Structural Data for complex 16 330
6-17. X-ray Structural Data for complex 17 351
6-18. X-ray Structural Data for complex 18 371
6-19. X-ray Structural Data for complex 19 392
6-20. X-ray Structural Data for complex 20 405
6-21. X-ray Structural Data for complex 21 418

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