一系列以[PNP]為配位基成功的合成四價鋯與鉿錯合物，丁基鋰先與[PNP]H形成[PNP]Li，再加入MCl4(THF)2 (M = Zr, Hf)即可成功合成產率約60%。透過格林那試劑成功得到一系列烷基取代的四價金屬錯合物[PNP]MR3 (R = Me, CH2SiMe3)或是[PNP]M(CH2SiMe3)2(E) (E = Cl, Me)，透過取代基的立體效應，可以控制並合成特定烷基取代的金屬錯合物。另外，實驗室所得的[PNP]MCl3晶體為雙金屬中心以氯原子架橋的七配位結構，若使用溶劑THF則可得到單金屬中心THF鍵結的七配位結構。透過磷原子變溫核磁共振光譜，可以得到不同立體效應或電子效應的取代對配位基[PNP]的流變行為。直接將烷基取代的錯合物[PNP]M(CH2SiMe3)2(Cl)加熱，即可進行分子內α-abstraction，得到alkylidene 錯合物 [PNP]M(=CHSiMe3)(Cl)，也成功得到alkylidene 錯合物 [PNP]H(=CHSiMe3)(CH2SiMe3)的晶體。控制不同溫度以NMR監測，透過Eyring plot分析得到[PNP]Zr(CH2SiMe3)2(Cl)進行 α-abstraction的∆H‡ = 16.49(19) kcal/mol以及∆S‡ = −25.64(19) cal/mol•K; [PNP]Hf(CH2SiMe3)2(Cl) α-abstraction的∆H‡ = 18.70(36) kcal/mol以及∆S‡ = −23.12(36) cal/mol•K。添加路易士酸AlMe3成功合成新的zwitterionic 錯合物 [PNP]Zr(μ2-CHSiMe3)2(AlMe2)，這個bisalkylidene錯合物也有完整的晶體及NMR的鑑定。第四族的alkylidene錯合物可以與具有雙鍵之烯類(乙烯、norbornene)進行複分解催化反應，尤其是[PNP]M(=CHSiMe3)(Cl)對norbornene開環岐化聚合有非常良好的立體選擇性，聚合物polynorbornene的立體位相選擇高達99%，且反應時間於兩小時內PDI值小於1.1。

A series of tetravalent zirconium and hafnium complexes were supported by diarylamido-phosphino [PNP]- (bis(o-diisopropylphosphinophenyl)amide) ligand. The reaction of MCl4(THF)2 (M = Zr, Hf) with [PNP]Li in toluene at room temperature generates [PNP]MCl3 as solid in 60 % yield. Polyalkyl complexes which are lack of β-hydrogen have been achieved in synthesis of [PNP]MR3 (R = Me, CH2SiMe3) or [PNP]M(CH2SiMe3)2(E) (E = Cl, Me) since we could control the desired product from steric effect. An X-ray diffraction study of [PNP]ZrCl3 showed it to be a chloride-bridged binuclear species {[PNP]MCl2(μ-Cl)}2 in which both metal atoms are 7-coordinate whereas that of [PNP]MCl3(THF) revealed a mononuclear, 7-coordinate core structure. The phosphine fluxional exchange were found in those complexes, monitoring variable temperature 31P NMR, their fluxionality were calculated by line shape analysis. By heating [PNP]M(CH2SiMe3)2(Cl) in solution, we can afford new alkylidene complexes [PNP]M(Cl)(=CHSiMe3) via intramolecular α-abstraction. Through Eyring plot analysis, the activation energy of [PNP]Zr(CH2SiMe3)2(Cl) α-abstraction is ∆H‡ = 16.49(19) kcal/mol and ∆S‡ = −25.64(19) cal/mol•K; [PNP]Hf(CH2SiMe3)2(Cl) α-abstraction is ∆H‡ = 18.70(36) kcal/mol and ∆S‡ = −23.12(36) cal/mol•K. The mixture [PNP]Hf(=CHSiMe3)(Cl) could not isolate with any purification, but [PNP]Hf(=CHSiMe3)(CH2SiMe3) obtained through directly alkylation. Here we also identified multiple alkylidene derivatives of [PNP]M(=CHSiMe3)(X) (X = Cl, CH2SiMe3). The X-ray structured and solution NMR data of those alkylidene complexes can be ascribed to evidence of α-agostic interaction with metal center. A novel zwitterionic complex [PNP]Zr(μ2-CHSiMe3)2(AlMe2) was characterized by X-ray and been received a bisalkylidene complex which was synthesized through addition Lewies acid (AlMe3) into [PNP]Zr(=CHSiMe3)(CH2SiMe3). Group 4 alkylidene was acting as catalyst to metathesize ethylene or norbornene. The complexes [PNP]M(=CHSiMe3)(Cl) have highly streotic selectivity catalyst for ring-opening metathesis polymerization (ROMP) of norbornene. It is important to emphasize the great significance of the catalyst discoveries and improvements for both academic research and industry.

論文審定書 I
誌謝 II
摘要 III
Abstract IV
Contents V
Figures Directory XIII
Table Directory XX
1. Introduction 1
1-1. C-H bond activation 1
1-2. Hybrid chelating ligands 4
1-3. Alkylidene complexes and multitude of applications olefin metathesis 6
2. Results and discussion 20
2-1. Synthesis, characterization, and fluxional behavior of [PNP]MCl3, [PNP]MCl3(THF) 20
2-1.1 Synthesis, characterization, and fluxional behavior of [PNP]ZrCl3, [PNP]ZrCl3(THF) 20
2-1.2 Synthesis, characterization, and fluxional behavior of [PNP]HfCl3, [PNP]HfCl3(THF) 24
2-2. Synthesis, and fluxional behavior of Group 4 polyalkyl complexes 29
2-2.1 Synthesis and fluxional behavior of trisalkyl zirconium complexes 30
2-2.2 Synthesis and fluxional behavior of trisalkyl of hafnium complexes 33
2-2.3 Synthesis and fluxional behavior of mixalkyl of zirconium complexes 35
2-2.4 Synthesis and fluxional behavior of mixalkyl of hafnium complexes 39
2-3. Synthesis, characterization, and kinetics investigation of alkylidene complex of Group 4 metal 42
2-3.1 Synthesis and kinetics investigation of [PNP]Zr(=CHSiMe3)(Cl) 42
2-3.2 Synthesis and kinetics investigation of [PNP]Zr(=CHSiMe3)(CH2SiMe3) 43
2-3.3 Synthesis, characterization, and kinetics investigation of [PNP]Hf(=CHSiMe3)(Cl) 44
2-3.4 Synthesis and characterization investigation of [PNP]Hf(=CHSiMe3)(CH2SiMe3) 47
2-4. C-H bond activation of alkylidene complexes 50
2-4.1 C-H bond activation of zirconium and hafnium alkylidene complexes 50
2-4.2 Olefin activation of zirconium alkylidene complexes 52
2-4.3 ROMP activation of zirconium alkylidene complexes 57
2-4.4 Olefin activation of hafnium alkylidene complexes 61
2-4.5 ROMP activation of hafnium alkylidene complexes 62
2-5. Reaction of zirconium alkylidene complex with electrophile 68
2-6. Theoretical studies of diarylamido-phosphino zirconium and hafnium complexes 73
2-6.1 Theoretical studies of {[PNP]MCl2(μ-Cl)}2, [PNP]MCl3(THF) electronic structure 73
2-6.2 Theoretical studies of alkylidene complex 77
2-6.3 Theoretical studies of alkylidene complexes electronic structure 83
2-6.4 Theoretical studies of bisalkylidene complex electronic structure 88
3. Conclusion 90
4. Experiment 91
4-1. General considerations 91
4-2. Instrument 91
4-3. Experiment 93
5. References 100
6. Appendix 107
6-1. Kinetic investigation of α-abstraction
6-2. Dynamic investigation of [PNP]− fluxionality 114
6-3. Synthesis and reactivity study of diarylamido-phosphino tantalum complexes 150
6-4. Theory mechanism studies of β-hydrogen elimination of [Ph-PNP]Ni(nBu) 152
6-4.1 Comparison of softwares and methods 153
7. X-ray crystal data 157

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