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, Ching-Han Hu, Chen Hsiung Hung, Hon Man Lee, Jui-Hsien Huang

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

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formic acid
Aluminum Compounds
Aluminum compounds
Carbon Disulfide
Carbon Dioxide
Isomers
Isocyanates
Methylene Chloride
X ray crystallography
Urethane
Toluene
Ether
Molecular structure
Density functional theory
Vacuum
Temperature
phenyl isocyanate

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

Cite this

@article{530ee8f657244b4d95210f2d421c684f,
title = "Hydroalumination of carbon dioxide, carbon disulfide, and phenyl isocyanate with an aluminum ketiminate compound",
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.",
author = "Kuo, {Pei Cheng} and Chen, {I. Chun} and Chang, {Jr Chiuan} and Lee, {Ming Tsung} and Ching-Han Hu and Hung, {Chen Hsiung} and Lee, {Hon Man} and Jui-Hsien Huang",
year = "2004",
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journal = "Chemische Berichte",
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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 journalArticle

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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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