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http://ir.ncue.edu.tw/ir/handle/987654321/10079
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| Title: | Hydroalumination of Carbon Dioxide, Carbon Disulfide, and Phenyl Isocyanate with an Aluminum Ketiminate Compound |
| Authors: | Kuo, P. C.;Chen, I. C.;Chang, J. C.;Lee, M. T.;Hu, Ching-Han;Hung, C. H.;Lee, H. M.;Huang, J. H. |
| Contributors: | 化學系 |
| Date: | 2004-12
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| Issue Date: | 2012-05-03T06:17:52Z
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| Publisher: | WILEY-VCH Verlag GmbH & Co. |
| 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. |
| Relation: | Eur. J. Inorg. Chem., 2004(24): 4898-4906 |
| Appears in Collections: | [化學系] 期刊論文
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