Hydroalumination of carbon dioxide, carbon disulfide, and phenyl isocyanate with an aluminum ketiminate compound

Pei Cheng Kuo, I. Chun Chen, Jr Chiuan Chang, Ming Tsung Lee, Chin Han Hu, Chen Hsiung Hung, Hon Man Lee, Jui Hsien Huang

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40 Citations (Scopus)


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 frans 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.

Original languageEnglish
Pages (from-to)4898-4906
Number of pages9
JournalEuropean Journal of Inorganic Chemistry
Issue number24
Publication statusPublished - 2004 Dec 17

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

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