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 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 language | English |
|---|---|
| Pages (from-to) | 4898-4906 |
| Number of pages | 9 |
| Journal | European Journal of Inorganic Chemistry |
| Issue number | 24 |
| DOIs | |
| Publication status | Published - 2004 Dec 17 |
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All Science Journal Classification (ASJC) codes
- Inorganic Chemistry
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Hydroalumination of carbon dioxide, carbon disulfide, and phenyl isocyanate with an aluminum ketiminate compound. / Kuo, Pei Cheng; Chen, I. Chun; Chang, Jr Chiuan; Lee, Ming Tsung; Hu, Ching-Han; Hung, Chen Hsiung; Lee, Hon Man; Huang, Jui-Hsien.
In: European Journal of Inorganic Chemistry, No. 24, 17.12.2004, p. 4898-4906.Research output: Contribution to journal › Article
TY - JOUR
T1 - Hydroalumination of carbon dioxide, carbon disulfide, and phenyl isocyanate with an aluminum ketiminate compound
AU - Kuo, Pei Cheng
AU - Chen, I. Chun
AU - Chang, Jr Chiuan
AU - Lee, Ming Tsung
AU - Hu, Ching-Han
AU - Hung, Chen Hsiung
AU - Lee, Hon Man
AU - Huang, Jui-Hsien
PY - 2004/12/17
Y1 - 2004/12/17
N2 - 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.
AB - 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.
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U2 - 10.1002/ejic.200400567
DO - 10.1002/ejic.200400567
M3 - Article
AN - SCOPUS:11244356068
SP - 4898
EP - 4906
JO - Chemische Berichte
JF - Chemische Berichte
SN - 0009-2940
IS - 24
ER -