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Please use this identifier to cite or link to this item: http://ir.ncue.edu.tw/ir/handle/987654321/14805

Title: 含雙陰離子口比咯與酮胺配位基之有機金屬錯合物的合成、鑑定、反應及應用(I)
Syntheses, Characterization, Reactivity, and Application of Organometallic Complexes Bearing Dianionic Pyrrolyl and Ketiminate Ligands (I)
Authors: 黃瑞賢
Contributors: 化學系
Keywords: 酮胺;;苯異�酸酯;開環;聚合
Dialuminum;Linked ketiminate;Diboron;Aluminum iodo
Date: 2004
Issue Date: 2012-12-10T01:41:14Z
Publisher: 行政院國家科學委員會
Abstract: 合成一系列含及酮胺雙陰離子配位基。其中在合成以環己烷基為架橋之雙酮胺雙陰離子配位基時,將使用順式及反式混合之環己烷二氨並加以分離。一系列含及酮胺雙陰離子配位基之烷基鋁化合物亦將被合成。這些新的化合物將被鑑定。計畫的第二年將合成一系列含配位基之氫鋁和氯化鋁化合物。此類氫鋁和氯化鋁化合物可以轉化成烷基鋁及相關之鋁化合物。經由加熱二烷基鋁或二氫鋁化合物,可以合成一系列含雙陰離子之雙鋁化合物。相同地,含架橋之酮胺配位基的雙核氫鋁和氯化鋁化合物亦可以被合成。再者,氫鋁和氯化鋁化合物與苯異酸酯、CO2、CO 以及其他有機小分子的反應也可以進行。也因此可以得到一系列插入及重排後的產物。另外我們亦將嘗試建立以氫鋁化合物為催化劑使CO2 形成甲酸之氫化循環反應。含烷氧基之鋁化合物可以經由除去烷類或氫氣而得。數種含砒及酮胺配位基之有機金屬化合物可以被合成,其中金屬包括Zn, In, Ga,和晚過度金屬如Fe, Ni, 和 Cu. 其中晚過度金屬化合物的應用在以後的計畫會在討論。在第三年的計畫中,己內醯胺和乳酸酐之開環聚合也會著手進行。聚合反應中,溶劑、溫度、單體/催化劑比例等變數將於與討論。聚合物之微型結構及其物性也將以1H, 13C NMR 光譜和GPC 加以鑑定。
Linked bis(ketimine) (1) can be prepared with the reaction of excess
2,4-pentandione and 4,4’-methylene-bis(2,6-diisopropylaniline) in methanol with
small amount of formic acid as catalysts. The dialuminum alkyl complexes
containing the linked bis(ketiminate) dianionic ligands,
[OC(Me)CHC(Me)N(2,6-iPr2C6H2-4)AlR2]2CH2 (2, R=Me; 3, R=Et), were prepared
by a reaction of 2 equiv AlR3 with [OC(Me)CHC(Me)NH(2,6-iPr2C6H2-4)]2CH2 in
methylene chloride. Reactions of 2 with 2 and 4 equiv of I2 gave corresponding
aluminum iodo complexes 4 and 5, respectively. Treatment of 5 with 2 equiv of
AgBF4, however, gave a diboron complex,
[OC(Me)CHC(Me)N(2,6-iPr2C6H2-4)BF2]2CH2 (6) in 18 % isolated yield. All new
complexes have been characterized by 1H and 13C NMR spectroscopy and complexes
2, 3, and 6 are also confirmed by X-ray diffraction.
Relation: 國科會計畫, 計畫編號: NSC93-2113-M018-005; 研究期間: 9308-9407
Appears in Collections:[化學系] 國科會計畫

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