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研究生:林加明
研究生(外文):Jia-ming Lin
論文名稱:二價鎳與二價鉑的雙(2-二苯基膦苯)醯胺錯合物
論文名稱(外文):Bis(2-diphenylphosphinophenyl)amide Complexes of Ni(II) and Pt(II)
指導教授:梁蘭昌
指導教授(外文):Liang Lan-Chang
學位類別:碩士
校院名稱:國立中山大學
系所名稱:化學系研究所
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2004
畢業學年度:92
語文別:英文
論文頁數:89
中文關鍵詞:醯胺錯合物
外文關鍵詞:amideplatinumnickelcomplexphosphine
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一系列二價鎳與二價鉑的雙(2-二苯基膦苯)醯胺錯合物已被合成,在對二價鎳一系列錯合物的研究中有以下發現。首先,含鹵基的錯合物 (包括氯化物、溴化物、碘化物) 可以在空氣中穩定存放。在含碳氫配位基的錯合物方面,我們也成功的合成出含烷基(alkyl)與芬基(aryl)配位基的錯合物。其中尤其以含有��-氫原子(��-hydrogen)的烷類錯合物受到矚目,原因在於這一類錯合物具有抵抗��-消去反應(��-elimination) 的能力。 氮、氧、硫等具有�鉆q子的元素一般而言是不容易與鎳形成錯合物,但在我們的研究中,確實能夠合成出具有醯胺基(amide)、酚基(phenolate)、硫酚基(thiophnolate)的鎳金屬錯合物。在鎳金屬的研究中還發現到含有鹵素的碳氫化合物會與[PNP]NiMe與[PNP]NiOTf經由活化碳與鹵素的鍵結(C-X bond)產生[PNP]NiX (X可為氯、溴、碘)。
在研究二價鉑的部分裡,我們成功合成出許多[PNP]NiX (X = Cl、Me、triflate、Ph)型態的錯合物。而利用[PNP]PtMe與B(C6F5)3或[PNP]PtOTf與Dabco活化苯的碳氫鍵的可行性也得到確認。
A series of nickel(II) and Pt(II) complexes supported by the bis(2-diphenylphosphinophenyl)amide ligand, [PNP]─ have been prepared.
In Nickel(II) chemistry, the halide complexes are both air and water stable. The nickel(II) alkyl and aryl derivatives were presented including those in which the alkyl contains ��-hydrogen atoms. A numbers of Amido, alkoxo, and thiolate complexes of nickel(II) were synthesized in an easy way. Hydrocarbons containing halogen react with [PNP]NiMe to generate [PNP]NiX (X = Cl, Br, I) via C-X bond activation, which was realized by multinuclear NMR spectroscopy.
In platinum(II) chemistry, complexes of chloride, triflate, alkyl, and aryl have been prepared. Benzene C-H bond activation is facilitated by the reaction of either [PNP]PtMe with B(C6F5)3 or [PNP]PtOTf with Dabco.
List of figures / VI
List of tables / VII
I. Introduction / 1
II. Experimental section / 4
i. Chemicals / 4
ii. Instrumentation / 7
iii. Synthesis / 9
1 Synthesis of [PNP]Li(THF)2 / 9
2 Synthesis of [PNP]NiCl / 10
3 Synthesis of [PNP]NiBr / 14
4 Synthesis of [PNP]NiI / 16
5 Synthesis of [PNP]NiMe / 18
6 Synthesis of [PNP]NiCH2Si(CH3)3 / 19
7 Synthesis of [PNP]NiPh / 20
8 Synthesis of [PNP]NiEt / 21
9 Synthesis of [PNP]NiiBu / 23
10 Synthesis of [PNP]NinBu / 24
11 Synthesis of [PNP]NiOtBu / 25
12 Synthesis of NaOPh / 26
13 Synthesis of [PNP]NiOPh / 27
14 Synthesis of NaSPh / 28
15 Synthesis of [PNP]NiSPh / 28
16 Synthesis of [PNP]NiNHPh / 30
17 Synthesis of [PNP]NiNHtBu / 31
18 Synthesis of [PNP]Ni(O2CPh) / 32
19 Synthesis of [PNP]NiOTf / 33
20 Synthesis of [(PNP)NiPy]OTf / 35
21 Synthesis of PtCl2(SMe2)2 / 36
22 Synthesis of [PNP]PtCl / 37
23 Synthesis of [PNP]PtMe / 38
24 Synthesis of [PNP]PtPh / 40
25 Synthesis of [PNP]PtOTf / 43
26 Synthesis of [(PNP)Pt(NCMe)]OTf / 44
27 Synthesis of [(PNP)PtPy]OTf / 45
28 Synthesis of [(PNP)Pt(dabco)]OTf / 46


III. Results and discussion / 47
i. Synthesis of lithium amide complex / 47
ii. Synthesis of [PNP]NiX complexes / 50
iii. Synthesis of [PNP]NiR complexes / 54
iv. Synthesis of amido, alkoxo, thiolate complexes / 57
v. Reactivity of [PNP]NiMe and [PNP]NiOTf / 59
vi. C-X bond activation / 61
vii. Synthesis of Pt(II) complexes / 65
IV. Conclusions / 69
V. References / 70
VI. Appendix / 74
i. Synthesis of [PNP]NiCCH / 74
ii. Synthesis of [PNP]PtnBU / 75
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