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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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 Hu, {Chin Han} and Hung, {Chen Hsiung} and Lee, {Hon Man} and Huang, {Jui Hsien}",
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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, Chin 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, Chin 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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