臺灣博碩士論文加值系統

一系列含有酮胺配位基與吡咯配位基單體、雙聚體與三聚體鈣金屬錯合物已被合成與鑑定。取Ca[N(SiMe3)2]2(THF)2與一當量與兩當量的HOCMeCHCMeNAr (Ar = 2,6-diisopropylphenyl) 酮胺配位基在甲苯中反應，分別可得到[Ca(OCMeCHCMeNAr){N(SiMe3)}]2 (1) 與 [Ca(-OCMeCHCMeNAr)(OCMeCHCMeNAr)]2 (2)。利用HOCMeCHCMeNAr 、Ca[N(SiMe3)2]2(THF)2與異丙醇進行原位反應，可得到三聚體鈣金屬烷氧錯合物Ca3(-OCMeCHCMeNAr)2(OCMeCHCMeNAr)(3-O-iPr)2(2-O-iPr) (3)。利用一當量的錯合物2與碘化鈣在四氫呋喃下迴流反應，進行配位基交換反應得到(OCMeCHCMeNAr)CaI(THF)3 (4)。取一當量的碘化鈣與酮胺配位基HOCMeCHCMeNAr 與HOCMeCHCMeNAr’ (Ar’ = 2-methoxylphenyl) 在四氫呋喃下反應可得到(OCMeCHCMeHNAr)2CaI2THF2 (5) 與(OCMeCHCMeHNAr’)2CaI2THF2 (6)。取Ca[N(SiMe3)2]2(THF)2與一當量 [C4H3NH(2-CH2NMe2)] 和[C4H3NH(2-CH2NEt2)] 在甲苯中反應，分別可得到雙聚體的{Ca[N(SiMe3)]{-1:5-[C4H3N(2-CH2NMe2)]}}2 (8) 和 {Ca[N(SiMe3)]{-1:5-[C4H3N(2-CH2NEt2)]}}2 (9)。錯合物9可在四氫呋喃下經由配位基再分配反應得到Ca[C4H3N(2-CH2NEt2)]2(THF)2 (10) 與 Ca[N(SiMe3)2]2(THF)2。錯合物10也可以用Ca[N(SiMe3)2]2(THF)2與兩當量C4H3NH(2-CH2NEt2) 在四氫呋喃反應得到。錯合物1、7、8與二苯基磷與苯乙烯進行分子間磷氫化反應。
一系列含有酮胺配位基四聚體鉀金屬錯合物已被合成與鑑定。取氫化鉀與一當量的HOCMeCHCMeNAr與HOCMeCHCMeNAr’ 在四氫呋喃中反應，分別可得到中心立方體[(OCMeCHCMeNAr)K]4THF4 (12) 與 [(OCMeCHCMeNAr’)K]4THF3 (13)
一系列含有酮胺配位基與吡咯配位基單體與雙聚體亞錫(II)金屬錯合物已被合成與鑑定。取Sn[N(SiMe3)2]2與一當量的 [C4H3NH(2-CH2NEt2)] 在甲苯中反應，可得到單體[C4H3NH(2-CH2NEt2)]SnN(SiMe3)2 (15)。取Sn[N(SiMe3)2]2與一當量的[C4H3NH(2-CH2NHtBu)]在甲苯中反應，可得到單體[Sn(μ-tBuNCH2-C4H3N)]2 (16)。取Sn[N(SiMe3)2]2與一當量與兩當量的HOCMeCHCMeNAr 酮胺配位基在甲苯中反應，分別可得到(OCMeCHCMeNAr)SnN(SiMe3)2 (17) 與 (OCMeCHCMeNAr)2Sn (18)。錯合物18可以與氯化鋁與三甲基鋁在甲苯中反應得到雙酮胺配位基鋁金屬錯合物。利用HOCMeCHCMeNAr、 Sn[N(SiMe3)2]2與2,6 –二甲基酚進行原位反應，可得到亞錫金屬烷氧錯合物(OCMeCHCMeNAr)Sn(O-2,6-dimethylphenyl) (19)。
所有新合成的錯合物除了錯合物4、14、19均有利用1H NMR及13C NMR 進行光譜鑑定，且錯合物1、2、3、4、5、6、7、8、9、10、12、13、14、15與16有利用X-ray進行結構上的鑑定。

A series of monomeric, dimeric and trimeric calcium complexes containing substituted pyrrolyl and ketiminate has been synthesized and characterized. Reactions of Ca[N(SiMe3)2]2(THF)2 with one and two equivalent of HOCMeCHCMeNAr (Ar = 2,6-diisopropylphenyl) yield in toluene [Ca(OCMeCHCMeNAr){N(SiMe3)}]2 (1) and [Ca(-OCMeCHCMeNAr)(OCMeCHCMeNAr)]2 (2), respectively. In situ reaction of HOCMeCHCMeNAr, Ca[N(SiMe3)2]2(THF)2, and isopropyl alcohol results a trimeric calcium alkoxides compound Ca3(-OCMeCHCMeNAr)2(OCMeCHCMeNAr)(3-O-iPr)2(2-O-iPr) (3).The reaction of 2 with two equivalent of CaI2 result in ligand exchanging to yield (OCMeCHCMeNAr)CaI(THF)4 (4).The reaction of CaI2 with one equivalent of HOCMeCHCMeNAr and HOCMeCHCMeNAr’ (Ar’ = 2-methoxylphenyl) in THF yield (OCMeCHCMeHNAr)2CaI2(THF)2 (5) and (OCMeCHCMeHNAr’)2CaI2(THF)2 (6).The reactions of Ca[N(SiMe3)2]2(THF)2 with one equivalent of [C4H3NH(2-CH2NMe2)] and [C4H3NH(2-CH2NEt2)] in toluene generates a dimeric {Ca[N(SiMe3)]{-1:5-[C4H3N(2-CH2NMe2)]}}2 (8) and {Ca[N(SiMe3)]{-1:5-[C4H3N(2-CH2NEt2)]}}2 (9) , respectively. Compound 9 was converted to Ca[C4H3N(2-CH2NEt2)]2(THF)2 (10) and Ca[N(SiMe3)2]2(THF)2 via ligand redistribution. 10 can also be obtained from the reaction in THF of Ca[N(SiMe3)2]2(THF)2 and two equiv of C4H3NH(2-CH2NEt2). Complexes 1、8、9 effect intermolecular hydrophosphination with diphenylphosphine and styrene.
A series of tetrameric potassium complexes containing substituted ketiminate has been synthesized and characterized. The reaction of KH with one equivalent HOCMeCHCMeNAr and HOCMeCHCMeNAr’ in THF yield cubic [(OCMeCHCMeNAr)K]4(THF)4 (12) and [(OCMeCHCMeNAr’)K]4(THF)3 (13) , respectively.
A series of monomeric and dimeric Sn(II) complexes containing substituted pyrrolyl and ketiminate has been synthesized and characterized. The reaction of Sn[N(SiMe3)2]2 with one equivalent [C4H3NH(2-CH2NEt2)] yield [C4H3NH(2-CH2NEt2)]SnN(SiMe3)2 (15). The reaction of Sn[N(SiMe3)2]2 with one equivalent [C4H3NH(2-CH2NHtBu)] yield dimeric [Sn(μ-tBuNCH2-C4H3N)]2 (16). The reaction of Sn[N(SiMe3)2]2 with one and two equivalent HOCMeCHCMeNAr yield (OCMeCHCMeNAr)SnN(SiMe3)2 (17) and (OCMeCHCMeNAr)2Sn (18) , respectively. Complex 18 react in toluene with AlCl3 and AlMe3 to form bisketiminate aluminum complexes. In situ reaction of HOCMeCHCMeNAr, Sn[N(SiMe3)2]2, and 2,6-dimethylphenol results a tin(II) alkoxide compound (OCMeCHCMeNAr)Sn(O-2,6-dimethylphenyl) (19)
All new complexes except 4、14、19 have been characterized by 1H NMR and 13C NMR spectroscopy and the structures of 1、2、3、4、5、6、7、8、9、10、12、13、14、15 and 16 have also been determined by X-ray crtystallographic studies.

章節 頁次
中文摘要
英文摘要
第一章 序論 1
第二章 實驗結果與討論 10
2-1 含酮胺配位基鈣金屬錯化合物的合成鑑定 10
2-2 含吡咯配位基鈣金屬錯化合物的合成鑑定 35
2-3 含酮胺配位基鉀金屬錯化合物的合成鑑定 47
2-4 含酮胺配位基與吡咯配位基亞錫金屬錯化合物的合成鑑定 62
第三章 凝固點下降測定研究 69
第四章 開環聚合反應 71
第五章 磷氫化反應 74
第六章 結論 77
第七章 實驗部分 78
7-1 一般實驗 78
7-2 物理性質測量 78
7-3 配位基與金屬起始物合成 78
7-3-1 合成 {Ca(OCMeCHCMeNAr)[N(SiMe3)]}2 (1) 79
7-3-2 合成 [Ca(-OCMeCHCMeNAr)(OCMeCHCMeNAr)]2 (2) 79
7-3-3 合成Ca3(-OCMeCHCMeNAr)2(OCMeCHCMeNAr)
(3-O-iPr)2(2-O-iPr) (3) 80
7-3-4 合成Ca(OCMeCHCMeNAr)I(THF)3 (4) 81
7-3-5 合成Ca(OSiPh3)2(THF)4 (5) 81
7-3-6 合成 (OCMeCHCMeHNAr)2CaI2(THF)2 (6) 81
7-3-7 合成 (OCMeCHCMeHNAr’)2CaI2(THF)2 (7) 82
7-3-8 合成 {Ca[N(SiMe3)]{-1:5-[C4H3N(2-CH2NMe2)]}}2 (8) 83
7-3-9 合成 {Ca[N(SiMe3)]{-1:5-[C4H3N(2-CH2NEt2)]}}2 (9) 83
7-3-10 合成 (DEAMP)2Ca(THF)2 (10) 84
7-3-11 合成 (BDMAMP)CaN(SiMe3)2 (11) 84
7-3-12 合成 [(OCMeCHCMeNAr)K]4(THF)4 (12) 85
7-3-13 合成 [(OCMeCHCMeNAr’)K]4(THF)3 (13) 85
7-3-15 合成 (DEAMP)SnN(SiMe3)2 (15) 86
7-3-16 合成 [Sn(μ-tBuNCH2-C4H3N)]2 (16) 86
7-3-17 合成 OCMeCHCMeNAr)SnN(SiMe3)2 (17) 87
7-3-18 合成(OCMeCHCMeNAr)Sn(O-2,6-dimethylphenyl) (19) 87
參考文獻 89
附錄 X-RAY DATA

圖次
頁次
圖 1-1 Simplified schematic materials cycle for biologically degradable materials based on renewable resources. 1
圖 2-1-1 The molecular structure of complex 1. 11
圖 2-1-2 The molecular structure of complex 2. 14
圖 2-1-3
1H NMR spectrum of complex 3 in C6D6 using 300 MHz NMR spectrometer. 17
圖 2-1-4 1H-13C HSQC NMR spectrum of complex 3 in C6D6 using 300 MHz NMRspectrometer. 18
圖 2-1-5 The molecular structure of complex 3. 19
圖 2-1-6 The molecular structure of complex 3. 21
圖 2-1-7 The molecular structure of complex 3. 22
圖 2-1-8 The molecular structure of complex 4. 24
圖 2-1-9 The molecular structure of complex 5. 27
圖 2-1-10 The molecular structure of complex 6. 31
圖 2-1-11 The molecular structure of complex 7. 32
圖 2-2-1 Variable-Temperature 1H NMR spectra of complex 9 in CD2Cl2 using 300 MHz NMR spectrometer. 36
圖 2-2-2 1H-13C HSQC NMR spectrum of complex 9 in CD2Cl2 using 300 MHz NMR spectrometer. 37
圖 2-2-3 The molecular structure of complex 8. 38
圖 2-2-4 The molecular structure of complex 9. 39
圖 2-2-5 Variable-Temperature 1H NMR spectra of complex 10 in C6D6 using 300 MHz NMR spectrometer. 42
圖 2-2-6 The molecular structure of complex 10. 43
圖 2-3-1 The molecular structure of complex 12. 48
圖 2-3-2 The molecular structure of complex 12. 51
圖 2-3-3 The molecular structure of complex 13. 52
圖 2-3-4 The molecular structure of complex 13. 55
圖 2-3-5 The molecular structure of complex 14. 57
圖 2-3-6 The molecular structure of complex 14. 58
圖 2-4-1 The molecular structure of complex 15. 63
圖 2-4-2 The molecular structure of complex 16. 64
圖 5-1 1H NMR spectrum of complex 8 with HPPh2 and styrene in C6D6 using 300 MHz NMR spectrometer. 75
圖 5-2 31P NMR spectrum of complex 8 with HPPh2 and styrene in C6D6 using 300 MHz NMR spectrometer. 75

表次 頁次
表 2-1-1 Selected Bond Distances (Å) and Angles (°) for Complex 1 12
表 2-1-2 Comparsion of Bond Distances (Å) of Complex 1 12
表 2-1-3 Selected Bond Distances (Å) and Angles (°) for Complex 2 15
表 2-1-4 Comparsion of Bond Distances (Å) of Complex 2 15
表 2-1-5 Selected Bond Distances (Å) and Angles (°) for Complex 3 19
表 2-1-6 Comparsion of Bond Distances (Å) of Complex 3 23
表 2-1-7 Selected Bond Distances (Å) and Angles (°) for Complex 4 25
表 2-1-8 Comparsion of Bond Distances (Å) of Complex 4 26
表 2-1-9 Selected Bond Distances (Å) and Angles (°) for Complex 5 28
表 2-1-10 Comparsion of Bond Distances (Å) of Complex 5 29
表 2-1-11 Selected Bond Distances (Å) and Angles (°) for Complex 6 31
表 2-1-12 Selected Bond Distances (Å) and Angles (°) for Complex 7 33
表 2-1-13 Comparsion of Bond Distances (Å) of Complexes 6 and 7 34
表 2-2-1 Selected Bond Distances (Å) and Angles (°) for Complex 8 38
表 2-2-2 Selected Bond Distances (Å) and Angles (°) for Complex 9 39
表 2-2-3 Comparsion of Bond Distances (Å) of Complexes 8 and 9 40
表 2-2-4 Selected Bond Distances(Å) and Angles(°) for Complex 10 43
表 2-2-5 Comparsion of Bond Distances (Å) of Complex 10 44
表 2-2-1 Selected Bond Distances (Å) and Angles (°) for Complex 12 48
表 2-3-2 Selected Bond Distances (Å) and Angles (°) for Complex 13 52
表 2-3-3 Comparsion of Bond Distances (Å) of Complexes 12 and 13 56
表 2-2-4 Selected Bond Distances (Å) and Angles (°) for Complex 14 58
表 2-4-1 Selected Bond Distances (Å) and Angles (°) for Complex 15 63
表 2-4-2 Selected Bond Distances (Å) and Angles (°) for Complex 16 65
表 3-1
Melting Point Depression Measurement Experimental Data of Complexes 1、8、9.
69
表 4-1
Polymerzation Data of ε-Caprolactone Catalyzed by
Potassium Complexes 12 and 13.
71
表 4-2
Polymerzation Data of ε-Caprolactone Catalyzed
by Calcium Complexes 3、8 and 9.
72
表 4-3
Polymerzation Data of L-Lactide Catalyzed by Calcium Complexes 12 and 13.
72
表 4-4
Polymerzation Data of L-Lactide Catalyzed by
Calcium Complexes 3、8 and 9.
73
表 5-1
Hydroamination Reaction of Styrene and
Diphenylphosphine Catalyzed by 1、8、9.
76

式次

頁次
Scheme 1-1 Chisholm實驗室發表二酮胺配位基鈣金屬錯合物 2
Scheme 1-2 Harder 實驗室發表二酮胺配位基鈣氫錯合物 3
Scheme 1-3
Harder 實驗室法表二酮胺配位基鈣氫錯合物與有機小分子反應
3
Scheme 1-4 Barrettm 與 Hill實驗室發表分子間氫磷化反應 4
Scheme 1-5 Roesky 實驗室發表的酮胺配位基鈣金屬錯合物 5
Scheme 1-6 Schumann 實驗室發表的吡咯配位基鈣金屬錯合物 6
Scheme 1-7 Ruhlandt-Senge 實驗室發表的吡咯配位基鈣金屬錯合物 6
Scheme 1-8 Gibson 實驗室發表的二酮胺配位基亞錫錯合物 7
Scheme 1-9 酮胺配位基與亞錫形成的一系列錯合物 8
Scheme 1-10 實驗室所用的配位基 9
Scheme 2-1-1 含酮胺配位基鈣金屬錯合物1、2、3之合成方程式 10
Scheme 2-1-2 含酮胺配位基鈣金屬錯合物4之合成方程式 23
Scheme 2-1-3 含酮胺配位基鈣金屬錯合物5之合成方程式 27
Scheme 2-1-4 含酮胺配位基鈣金屬錯合物6、7之合成方程式 30
Scheme 2-2-1 含吡咯配位基鈣金屬錯合物8、9之合成方程式 35
Scheme 2-2-2 含吡咯配位基鈣金屬錯合物10之合成方程式 41
Scheme 2-2-3 錯合物9與四氫呋喃反應形成錯合物10之方程式 45
Scheme 2-2-1 含吡咯配位基鈣金屬錯合物11之合成方程式 45
Scheme 2-3-1 含酮胺配位基鉀金屬錯合物12、13之合成方程式 47
Scheme 2-3-2 含酮胺配位基鉀金屬錯合物14之合成方程式 57
Scheme 2-4-1 含吡咯配位基亞錫金屬錯合物15、16之合成方程式 62
Scheme 2-4-2 含酮胺配位基亞錫金屬錯合物17、18之合成方程式 66
Scheme 2-4-3 錯合物18與金屬鹵化物反應方程式 67
Scheme 2-4-4 含酮胺配位基亞錫金屬錯合物19之合成方程式 68
Scheme 3-1 錯合物8、9單體與雙聚體變動方程式 70
Scheme 5-1 鈣金屬磷氫化反應方程式 74

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