臺灣博碩士論文加值系統

一系列含對稱及不對稱參牙基吡咯衍生物的金屬錯化合物(金屬：鋯、鉿)已經被合成與鑑定。取M(NR2)4(1, M = Zr，R = Me；2, M = Zr，R = Et)與一倍量[C4H2NH(2-CH2NHtBu)(5-CH2NMe2)]在正庚烷下反應三小時，合成Zr[C4H2N(2-CH2NtBu)(5-CH2NMe2)](NR2)2 (4, R = Me；5, R = Et)。取M(NEt2)4 (2, M = Zr；3, M = Hf)與兩倍量[C4H2NH(2-
CH2NHtBu)(5-CH2NMe2)]在二氯甲烷下反應十二小時，合成MCl[C4H2N(2-CH2NHtBu)(5-CH2NMe2)][C4H2N(2-CH2NtBu)(5-CH2NMe2)](6, M = Zr；7, M = Hf)。取1與[C4H2NH(2,5-CH2NHtBu)]在乙醚下反應十四小時，合成Zr[C4H2N(2-CH2NtBu)(5-CH2NHtBu)](N-
Me2)2(12)。我們以PhNCO、PhNCS及CS2對錯化合物4、5及12進行嵌入反應。錯化合物4、5與一倍量PhNCO在乙醚中反應可以得到Zr[C4H2N(2-CH2NtBu)(5-CH2NMe2)][PhNC(NR2)O](NR2)(8, R = Me；9, R = Et)，錯化合物4與一倍量PhNCS在乙醚中反應可得到Zr[C4H2N(2-CH2NtBu)(5-CH2NMe2)][PhNC(NMe2)S](NMe2)(10)錯化合物12與一倍量CS2在乙醚下反應可得到Zr[C4H2N(2-CH2NtBu)(5-
CH2NHtBu)][CS(NMe2)C](NMe2)(13)。錯化合物5與兩倍量PhNC(NEt2)OH在乙醚下反應可得到三倍量產物Zr[C4H2N(2-CH2NH
tBu)(5-CH2NMe2)][PhNC(NEt2)O]3(11)
所有新合成的金屬錯化合物均有利用1H及13C NMR進行光譜的鑑定，而6、7、10、11及13有利用X-ray進行結構上的鑑定。錯化合物5、6、8及12均對乙烯進行催化反應，以探討其催化活性與反應性。

A series of zirconium and hafnium complexes containing symmetric and asymmetric tridentate substituted pyrrolyl ligand have been synthesizd and characterized. The zirconium compounds Zr[C4H2N(2-CH2NtBu)(5-CH2NMe2)](NR2)2 (4, R = Me；5, R = Et) have been prepared by reacting M(NR2)4(1, M = Zr，R = Me；2, M = Zr，R = Et) with 1 equiv of [C4H2NH(2-CH2NHtBu)(5-CH2NMe2)] in heptane via deamination. MCl[C4H2N(2-CH2NHtBu)(5-CH2NMe2)][C4H2N(2-CH2N-tBu)(5-CH2NMe2)](6, M = Zr；7, M = Hf) have been prepared by reacting M(NEt2)4 (2, M = Zr 3, M = Hf) with 2 equiv of [C4H2NH(2-CH2NHtBu)(5-CH2NMe2)] in CH2Cl2 via deamination, and Zr[C4H2N(2-CH2NtBu)(5-CH2NHtBu)](NMe2)2(12) have been prepared by reacting 1 with 1 equiv [C4H2NH(2,5-CH2NHtBu)] in ether via deamination. The insertion reaction of PhNCO, PhNCS and CS2 with complexes 4, 5 and 12 have been studied. The zirconium compounds Zr[C4H2N(2-CH2NtBu)(5-CH2NMe2)][PhNC(NR2)O](NR2)(8, R = Me；9, R = Et) have been prepared by reacting 4 and 5 with 1 equiv PhNCO in ether. Zr[C4H2N(2-CH2NtBu)(5-CH2NMe2)][PhNC(NMe2)S](NMe2)(10) have been prepared by reacting 4 with 1 equiv PhNCS in ether. Zr[C4H2N(2-CH2NtBu)(5-CH2NHtBu)][CS(NMe2)C](NMe2)(13) have been prepared by reacting 12 with 1 equiv CS2 in ether, and Zr[C4H2N(2-CH2NHtBu)(5-CH2NMe2)][PhNC(NEt2)O]3(11) have been prepared by reacting 5 with 2 equiv PhNC(NEt2)OH in ether.
All the new compounds were characterized by 1H and 13C NMR spectroscopy and the structures of 6, 7 , 10, 11 and 13 have also been determined by X-ray crystallographic studies. Complexes 5, 6, 8 and 12 have been studied as olefin polymerization of ethane.

章節 頁次
中文摘要
英文摘要
第一章
緒論 1
1-1 烯類聚合反應 1
1-2 開環聚合反應 7
第二章
結果與討論
合成不對稱參牙吡咯衍生物配位基[C4H2NH(2-CH2NHtBu)(5-
CH2NMe2)] 10
2-1 含不對稱參牙基吡咯衍生物金屬錯化合物之合成與鑑定 11

2-1-1 Zr[C4H2N(2-CH2NtBu)(5-CH2NMe2)](NMe2)2(4) 12

2-1-2 Zr[C4H2N(2-CH2NtBu)(5-CH2NMe2)](NEt2)2(5) 12

2-1-3 ZrCl[C4H2N(2-CH2NtBu)(5-CH2NMe2)][C4H2N(2-CH2
NHtBu)(5-CH2NMe2)](6) 13

2-1-4 HfCl[C4H2N(2-CH2NtBu)(5-CH2NMe2)][C4H2N(2-CH2
NHtBu)(5-CH2NMe2)](7) 19

2-2含不對稱參牙基吡咯衍生物金屬錯化合物與異氰酸苯酯(PhNCO)
及異硫氰酸苯酯(PhNCS)之嵌入反應及脫氫反應 22

2-2-1Zr[C4H2N(2-CH2NtBu)(5-CH2NMe2)][PhNC(NEt2)O]-
(NEt2)(8) 23

2-2-2Zr[C4H2N(2-CH2NtBu)(5-CH2NMe2)][PhNC(NMe2)O]-
(NMe2)(9) 24

2-2-3Zr[C4H2N(2-CH2NtBu)(5-CH2NMe2)][PhNC(NMe2)S]-
(NMe2)(10) 28

2-2-4Zr[C4H2N(2-CH2NHtBu)(5-CH2NMe2)][PhNC(NEt2)-
O]3(11) 28

合成對稱參牙吡咯衍生物配位基[C4H2NH(2,5-CH2NH
tBu)] 33

2-3含對稱參牙基吡咯衍生物金屬錯化合物之合成與鑑定 33

2-3-1Zr[C4H2N(2-CH2NtBu)(5-CH2NHtBu)](NMe2)2(12) 34

2-3-2Zr[C4H2N(2-CH2NtBu)(5-CH2NHtBu)][CS(NMe2)C]
(NMe2)(13) 36

第三章 鋯金屬錯化合物之聚合反應 38

3-1鋯金屬錯化合物對乙烯聚合反應 38

第四章 結論 40

第五章 實驗部分 41

第一節 一般實驗 41

第二節 物理性質的測量 41

第三節 不對稱參牙基吡咯衍生物配位基鋁金屬錯合物的合成 42

5-3-1合成Zr[C4H2N(2-CH2NtBu)(5-CH2NMe2)](NMe2)2(4) 42

5-3-2合成Zr[C4H2N(2-CH2NtBu)(5-CH2NMe2)](NEt2)2(5) 43

5-3-3合成ZrCl[C4H2N(2-CH2NHtBu)(5-CH2NMe2)][C4H2N(2-
CH2NtBu)(5CH2NMe2)](6) 44

5-3-4合成HfCl[C4H2N(2-CH2NHtBu)(5-CH2NMe2)][C4H2N(2-
CH2NtBu)(5-CH2NMe2)](7) 45

5-3-5合成Zr[C4H2N(2-CH2NtBu)(5-CH2NMe2)][PhNC(NEt2)-
O](NEt2)(8) 47

5-3-6合成Zr[C4H2N(2-CH2NtBu)(5-CH2NMe2)][PhNC(NMe2)
O](NMe2)(9) 48

5-3-7合成Zr[C4H2N(2-CH2NtBu)(5-CH2NMe2)][PhNC(NMe2)S]
(NMe2)(10) 49

5-3-8合成Zr[C4H2N(2-CH2NHtBu)(5-CH2NMe2)][PhNC(NEt2)-
O]3(11) 50

5-3-9合成Zr[C4H2N(2-CH2NtBu)(5-CH2NHtBu)](NMe2)2(12)51

5-3-10合成Zr[C4H2N(2-CH2NtBu)(5-CH2NHtBu)][CS(NMe2)C]-
(NMe2)(13) 52

參考資料 53

附錄　X-Ray Data 56
圖次
圖1-2-1
Practical application of the biodegradable polymers based on lactic and glycolic acids
8
圖2-1-1
Homonuclear decoupling of 1H NMR spectra of complex 6 in C6D6 using 300MHz NMR spectrometer
16
圖2-1-2
1H-13C HSQC 2D NMR spectrum of complex 6 in C6D6 using 300MHz NMR spectrometer
17
圖2-1-3
The molecular structure of complex 6
18
圖2-1-4
The molecular structure of complex 7
21
圖2-2-1
1H-13C HSQC 2D NMR spectrum of complex 10 in C6D6 using 300MHz NMR spectrometer
26
圖2-2-2
The molecular structure of complex 10
27
圖2-2-3
Variable-temperature NMR spectra of complex 11 in d8-toluene using 300MHz NMR spectrometer
30
圖2-2-4
The molecular structure of complex 11
31
圖2-3-1
Variable-temperature NMR spectra of complex 12 in d8-toluene using 300MHz NMR spectrometer
35
圖2-3-2
The molecular structure of complex 13
36
表次
表2-1-1
錯化合物6中心金屬周圍鍵長( Å )與鍵角( ° )
18
表2-1-2
錯化合物7中心金屬周圍鍵長( Å )與鍵角( ° )
21
表2-2-1
錯化合物10中心金屬周圍鍵長( Å )與鍵角( ° )
27
表2-2-2
錯化合物11中心金屬周圍鍵長( Å )與鍵角( ° )
31
表2-3-1
錯化合物13中心金屬周圍鍵長( Å )與鍵角( ° )
37
表3-1-1
乙烯聚合反應數據表
38
表3-1-2
文獻中乙烯聚合反應數據表
39
式次
Scheme 1-1-1
TiCl4與AlMe3共催化乙烯反應
2
Scheme 1-1-2
Metallocenes與MAO共催化途徑
3
Scheme 1-1-3
取代基不同合成出不同立體選擇性的聚乙烯
3
Scheme 1-1-4
CGC結構
4
Scheme 1-1-5
β-二酮胺、酮胺和希夫鹼等系統配位基
4
Scheme 1-1-6
含有兩倍量酮胺配位基的鋁氫化物的合成
5
Scheme 1-1-7
鈦金屬錯化合物與B(C6F5)3共催化丙烯
5
Scheme 1-1-8
Coates發表以Schiff Base為配位基的鈦金屬錯化合物對於乙烯與丙烯的聚合反應
6
Scheme 1-1-9
烯類聚合催化之反應機構
7
Scheme 1-2-1
開環聚合反應之反應機構
8
Scheme 1-2-2
對稱與不對稱參牙基吡咯衍生物配位基
9
Scheme 2-1
合成不對稱參牙吡咯衍生物配位基[C4H2NH(2-CH2NH- tBu)(5-CH2NMe2)]
10
Scheme 2-1-1
錯化合物4、5、6及7之合成反應方程式
11
Scheme 2-1-2
錯化合物6形成推測反應機制
14
Scheme 2-2-1
錯化合物8、9、10及11之合成反應方程式
23
Scheme 2-2-2
合成類尿素配位基PhNC(NEt2)OH
23
Scheme 2-2-3Zr與類尿素配位基團共振模式24
Scheme 2-2-4錯化合物11形成推測反應機制29
Scheme 2-3合成對稱參牙吡咯衍生物配位基[C4H2NH(2,5-CH2NH- tBu)]33
Scheme 2-3-1錯化合物12及13之合成反應方程式34
Scheme 3-1-1文獻中進行乙烯催化反應之鋯金屬錯化合物39

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