利用本實驗室所合成出的{[O3P]AlMe}Li(DME)3分別與銀(Ag)及鉈(Tl)金屬化合物進行反應，可以分別得到{[O3P]AlMe}Ag和{[O3P]AlMe}Tl，利用不同核種的核磁共振(NMR)光譜及元素分析(EA)對其加以鑑定，並比較三個錯合物中金屬與磷(P)原子之間的作用力(interaction)，{[O3P]AlMe}Li(DME)3在31P NMR中無法看到Li與P原子之間的耦合(coupling)，然而{[O3P]AlMe}Ag或{[O3P]AlMe}Tl可在31P NMR中分別觀察到Ag或Tl與P原子之間的耦合。將三苯酚磷化物2,2′,2′′-phosphinotris(4,6-di-tert-butylphenlate) ([O3P]3-)當作配位基與釔(Y)金屬化合物反應，可以得到[O3PH]YCl，利用不同核種的NMR鑑定之。我們以雙苯酚磷化物2,2′-phenylphosphinobis(4,6-di-tert-butylphenlate) ([OPO]2-)及三苯酚磷化物分別在THF溶液中與鋅(Zn)金屬化合物反應，可分別得到{[OPO]Zn}2及{[O3P]Zn}2Zn(THF)2，利用不同核種的NMR及X-ray繞射鑑定其組成。
將本實驗室已發表的三牙胺基膦化物配位基bis(2-diphenylphosphinophenyl)amide, [Ph-PNP]-，和bis(2-diisopropylphosphinophenyl)amide，[iPr-PNP]-，分別與鉈(Tl)金屬化合物反應，得到兩個Tl金屬錯合物[R-PNP]Tl (R = Ph or iPr)利用不同核種的NMR鑑定，在31P{1H} NMR中觀察到P與Tl原子之間的耦合(coupling)，可以確定兩原子之間確實有鍵結(bonding)。
我們以Pd(OAc)2當作催化劑利用cross-coupling的策略合成具有剛硬苯環骨架的胺基氯化物N-(2-chlorophenyl)-2,6-diisopropylaniline，H[iPrAr-NCl]，接著將此氯化物溶在toluene溶液中降溫至-35 °C 與等當量的n-BuLi反應得到[iPrAr-NCl]Li，將其溶於diethyl ether中做再結晶可得到含兩分子diethyl ether配位的[iPrAr-NCl]Li(OEt2)2無色晶體，利用X-ray繞射鑑定可看出其結構為中心金屬Li與胺基氯化物上的N和Cl原子及兩個diethyl ether分子的O原子形成四配位的Li金屬錯合物。

The Complexes {[O3P]AlMe}Ag and {[O3P]AlMe}Tl have been synthesized and characterized successfully. The structures of {[O3P]AlMe}Ag and {[O3P]AlMe}Tl were compared with the reported {[O3P]AlMe}Li(DME)3. The 31P NMR showed that soft nature of Ag and Tl ions in {[O3P]AlMe}Ag and {[O3P]AlMe}Tl respectively is interacted with P atom of phenolato ligand and the hard Li ion did not interact with P atom. The reaction of H3[O3P] with YCl3 at RT gave [O3PH]YCl. This is confirmed by 1H NMR technique. The complexes {[O3P]Zn}2Zn(THF)2 and {[OPO]Zn}2 were prepared by the reaction of Zn salt with [O3P]3- and [OPO]2- respectively in excellent yield and characterized by 1H NMR spectroscopy. The X-ray structure of complex {[O3P]Zn}2Zn(THF)2 reveals that it is formed as trimer.
We have prepared two thallium complexes derived from diarylamido-based PNP ligands and TlOTf. 31P{1H} NMR revealed that two phosphine atoms in PNP ligand is coordinated with metal Tl center.
The palladium-catalyzed aryl amination of 1-bromo-2-chlorobenzene with 2,6-diiso- propylaniline quantitatively produces N-(2-chlorophenyl)-2,6-diisopropylaniline, H[iPrAr- NCl]. Deprotonation of H[iPrAr-NCl] with 1 equiv of n-BuLi in toluene at -35 °C produced cleanly [iPrAr-NCl]Li. Subsequent recrystallization of [iPrAr-NCl]Li in diethyl ether generated the bis(ether) adduct [iPrAr-NCl]Li(OEt2)2. An X-ray study of [iPrAr-NCl]Li- (OEt2)2 showed it to be a four-coordinate species with the coordination of the chlorine atom to the lithium center.

壹、苯酚膦化物銀、鉈、釔、鋅錯合物.............................1
一、緒論................................................................................1
二、結果與討論....................................................................3
1.{[O3P]AlMe}Ag的合成與鑑定.........................................3
2.{[O3P]AlMe}Tl的合成與鑑定...........................................4
3.[O3PH]YCl的合成與鑑定................................................7
4.{[O3P]Zn}2Zn(THF)2的合成與鑑定..............................8
5.{[OPO]Zn}2的合成與鑑定.............................................11
三、結論.............................................................................12
四、實驗部分.....................................................................13
1.一般程序.........................................................................13
2.儀器.................................................................................14
3.實驗步驟.........................................................................15
(1)合成{[O3P]AlMe}Ag....................................................15
(2)合成{[O3P]AlMe}Tl......................................................15
(3)合成TlOTf.....................................................................16
(4)合成[O3PH]YCl...........................................................16
(5)合成{[O3P]Zn}2Zn(THF)2.........................................17
(6)合成{[OPO]Zn}2..........................................................18
五、參考文獻.....................................................................19
貳、胺基膦化物鉈錯合物..................................................21
一、緒論.............................................................................21
二、結果與討論.................................................................22
1.[iPr-PNP]Tl的合成與鑑定.............................................22
2.[Ph-PNP]Tl的合成與鑑定.............................................23
三、結論.............................................................................24
四、實驗部分.....................................................................25
1.一般程序.........................................................................25
2.儀器.................................................................................25
3.實驗步驟.........................................................................26
(1)合成[iPr-PNP]Tl..........................................................26
(2)合成[Ph-PNP]Tl..........................................................27
五、參考文獻.....................................................................28
參、胺基氯化物鋰錯合物..................................................30
一、緒論.............................................................................30
二、結果與討論.................................................................31
1.H[iPrAr-NCl]的合成與鑑定...........................................31
2.[iPrAr-NCl]Li的合成與鑑定...........................................32
3.[iPrAr-NCl]Li(OEt2)2的合成與鑑定.............................33
三、結論.............................................................................34
四、實驗部分.....................................................................34
1.一般程序.........................................................................34
2.儀器.................................................................................35
3.實驗步驟.........................................................................36
(1)合成H[iPrAr-NCl]........................................................36
(2)合成[iPrAr-NCl]Li........................................................37
(3)合成[iPrAr-NCl]Li(OEt2)2..........................................38
五、參考文獻.....................................................................38
肆、附錄..............................................................................40
一、其他化合物的合成與鑑定.........................................40
1.合成[OPO]2NbOH.........................................................40
2.合成Nb(O)Cl3(THF)2...................................................40
3.合成H2[OPO]S..............................................................41
4.合成H2[O3PMe]............................................................41
5.合成H[iPr(ArF)N]...........................................................42
二、參考文獻.....................................................................43
三、變溫NMR光譜圖........................................................44
1.[Ph-PNP]Tl的變溫31P{1H} NMR光譜.......................44
2.[OPO]2NbOH的變溫1H NMR光譜.............................47
四、Crystallographic Data..............................................50

壹、苯酚膦化物銀、鉈、釔、鋅錯合物
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5. 將Zn (1.1716 g, 18.5 mmol)置於Schlenk-flask中，膜口處塞septa後纏銅線，在side arm處抽灌氮氣三次，加入經過除水的THF(20 mL)，再加入1,2-dibromoethane (0.08 mL, 0.9241 mmol)，接著加熱至THF沸騰後使其降溫至室溫，共4次循環，最後再加入Me3SiCl (0.02 mL, 0.1576 mmol)並在室溫下攪拌15分鐘後，靜置，將THF移走，抽乾，即可得到活化過的Zn dust。