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Please use this identifier to cite or link to this item: http://ir.ncue.edu.tw/ir/handle/987654321/14776

Title: Hydroalumination of Carbon Dioxide, Carbon Disulfide, and Phenyl Isocyanate with an Aluminum Ketiminate Compound
Authors: Kuo, Pei-Cheng;Chen, I-Chun;Chang, Jr-Chiuan;Lee, Ming-Chung;Hu, Chin-Han;Hung, Chen-Hsiung;Lee, Hon-Man;Huang, Jui-Hsien
Contributors: 化學系
Date: 2004-12
Issue Date: 2012-12-10T01:39:37Z
Publisher: Wiley-VCH Verlag GmbH & Co. KGaA
Abstract: 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)
Relation: Eur. J. Inorg. Chem., 2004(24): 4898-4906
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