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http://ir.ncue.edu.tw/ir/handle/987654321/14776
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題名: | Hydroalumination of Carbon Dioxide, Carbon Disulfide, and Phenyl Isocyanate with an Aluminum Ketiminate Compound |
作者: | Kuo, Pei-Cheng;Chen, I-Chun;Chang, Jr-Chiuan;Lee, Ming-Chung;Hu, Chin-Han;Hung, Chen-Hsiung;Lee, Hon-Man;Huang, Jui-Hsien |
貢獻者: | 化學系 |
日期: | 2004-12
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上傳時間: | 2012-12-10T01:39:37Z
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出版者: | Wiley-VCH Verlag GmbH & Co. KGaA |
摘要: | The reaction of MeC(O)C(H)=C(Me)NHAr (Ar = 2,6-diisopropylphenyl) (1) with excess LiAlH4 in diethyl ether at −78 °C generates [AlH(OCMeCHCMeNAr)2] (2) in 76% yield. The aluminum formate compound [Al(OCMeCHCMeNAr)2(OCOH)] (3) can be isolated from the reaction of 2 with CO2 in 93% yield. Compound 3 is thermally stable and remains unchanged when heated under vacuum at 100 °C for 24 h. Similarly, a solution of 2 in dichloromethane reacts with carbon disulfide or phenyl isocyanate at room temperature to yield the insertion products [Al(OCMeCHCMeNAr)2(SCHS)] (4) and [Al(OCMeCHCMeNAr)2(OCH=NPh)] (5), respectively, in 80% and 92% yield. Reaction of 2 with 1 equiv. of urethane in toluene at refluxing temperature for 1 h yields the aluminum isocyanate compound [Al(OCMeCHCMeNAr)2(NCO)] (6). The molecular structures of compounds 2−6 have been determined by X-ray crystallography. Density functional calculations show that the isomer of compound 2 with an N−N trans arrangement is 3.1 kcal·mol−1 lower in energy than the O−O trans isomer. Inserting CO2 into the Al−H bond of compound 2 results in the formation of the formate compound 3; this reaction is predicted to be exothermic by 29.8 kcal·mol−1. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) |
關聯: | Eur. J. Inorg. Chem., 2004(24): 4898-4906 |
顯示於類別: | [化學系] 期刊論文
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