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Title: 含具取代之砒各配位基之13族化合物的合成,反應以及聚合反應
Synthesis, Reactivity and Polymerization of Group 13 Metal Complexes (M=Al, Ga, In) Containing Substituted Pyrrolated Ligands
Authors: 黃瑞賢
Contributors: 化學系
Keywords: 砒咯;配位基;錯合物;;;
Date: 2001
Issue Date: 2012-12-10T01:40:41Z
Publisher: 行政院國家科學委員會
Abstract: GaCl3 與 Li[NC4H3(CH2NMe2)-2] (n =
1, 2, 3) 於乙醚中並在–78 °C 下反應產生
GaCl3-n[NC4H3(CH2NMe2)-2]n (n=1, 1; n=2,
2; n=3, 3)。 化合物1 與兩當量之 RLi
反應, 經由金屬交換反應而產生
GaR2[NC4H3(CH2NMe2)-2] (4a, R=Me; 4b,
R=Bu)。 當2 與一當量之RLi 於乙醚中
反應, 3 和4 會經由配位基的交換而產
生。. 由變溫1H NMR 光譜實驗得知,
五配位之化合物3 於溶液中會進行轉換
而在 5 °C 時會得到合併點。其DG¹ 約為
10.4 Kcal/mole. 首有之化合物均經由1H
和13C NMR 光譜鑑定。化合物3 和4a
亦經由X 光繞射一件定期結構。
Treatment of GaCl3
Li[NC4H3(CH2NMe2)-2] (n = 1, 2, 3) in
diethyl ether at –78 °C yields
GaCl3-n[NC4H3(CH2NMe2)-2]n (n=1, 1; n=2,
2; n=3, 3). Compound 1 reacts with two
equiv of RLi to afford
GaR2[NC4H3(CH2NMe2)-2] (4a, R=Me; 4b,
R=Bu) via transmetallation. Reacting 2
with one equiv of RLi in diethyl ether, 3 and
4 are formed via ligand redistribution.
Variable temperature 1H NMR spectroscopic
experiments reveal that the five-coordinate
gallium compound 3 is fluxional and results
in a coalescence temperature at 5 °C, at
which DG¹ is calculated at ca. 10.4
Kcal/mole. All the new compounds have
been characterized by 1H and 13C NMR
spectroscopy and the structures of
compounds 3 and 4a have also been
determined by X-ray crystallography.
Relation: 國科會計畫, 計畫編號: NSC90-2113-M018-003; 研究期間: 9008-9107
Appears in Collections:[化學系] 國科會計畫

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