Metal-Induced Coordination Inversion and Carbon-Nitrogen Bond Rearrangement. Structurally Characterized Phenyl Isocyanate Inserted into Aluminum Methyl Compounds and O- and N-Bound Aluminum Compounds

Chia Fu Tsai, Hsing Jen Chen, Jr Chiuan Chang, Cheng Hsiang Hung, Chun Chia Lai, Ching Han Hu, Jui Hsien Huang

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Abstract

[C4H3N(CH2NMe2)-2]AlMe 2 (1) is prepared in 88% yield by the reaction of substituted pyrrole [C4H4N(CH2NMe2)-2] with 1 equiv of AlMe3 in methylene chloride. Reaction of compound 1 with 1 equiv of phenyl isocyanate in toluene generates a seven-membered cycloaluminum compound {C4H3N[CH2NPh(CONMe 2)]-2}AlMe2 (2). The phenyl isocyanate was inserted into the aluminum and dimethylamino nitrogen bond and induced an unusual rearrangement which results in C-N bond breaking and formation. A control experiment shows that the reaction of substituted pyrrole [C4H 4N(CH2NMe2)-2] with 1 equiv of phenyl isocyanate in diethyl ether yields a pyrrolyl attached urea derivative {C 4H3N(CH2NMe2)-2-[C(=O)NHPh]-1} (3). The demethanation reaction of AlMe3 with 1 equiv of 3 in methylene chloride at 0 °C afforded O-bounded and N-bounded aluminum dimethyl compounds {C4H3N(CH2-NMe 2)-2-[C(=O)NPh]-1}AlMe2 (4a) and {C4H 3N(CH2NMe2)-2-[CO(=NPh)]-1}AlMe2 (4b) in a total 78% yield after recrystallization. Both 4a and 4b are observed in 1H NMR spectra; however, the relative ratio of 4a and 4b depends on the solvent used. Two equivalents of AlMe3 was reacted with 3 in methylene chloride to yield a dinuclear aluminum compound AlMe 3{C4H3N(CH2NMe 2)-2-[C(=O)NPh]-1}AlMe2 (5). Reaction of 5 with another equivalent of ligand 3 results in the re-formation of compounds 4a and 4b.

Original languageEnglish
Pages (from-to)2183-2188
Number of pages6
JournalInorganic Chemistry
Volume43
Issue number6
Publication statusPublished - 2004 Mar 22

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Aluminum Compounds
methyl compounds
aluminum compounds
isocyanates
Methylene Chloride
Aluminum
Pyrroles
Nitrogen
Carbon
Metals
inversions
aluminum
nitrogen
methylene
carbon
metals
chlorides
pyrroles
Toluene
Carbon Monoxide

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

@article{9159d83c6f304e3aab48f0be7b1a939c,
title = "Metal-Induced Coordination Inversion and Carbon-Nitrogen Bond Rearrangement. Structurally Characterized Phenyl Isocyanate Inserted into Aluminum Methyl Compounds and O- and N-Bound Aluminum Compounds",
abstract = "[C4H3N(CH2NMe2)-2]AlMe 2 (1) is prepared in 88{\%} yield by the reaction of substituted pyrrole [C4H4N(CH2NMe2)-2] with 1 equiv of AlMe3 in methylene chloride. Reaction of compound 1 with 1 equiv of phenyl isocyanate in toluene generates a seven-membered cycloaluminum compound {C4H3N[CH2NPh(CONMe 2)]-2}AlMe2 (2). The phenyl isocyanate was inserted into the aluminum and dimethylamino nitrogen bond and induced an unusual rearrangement which results in C-N bond breaking and formation. A control experiment shows that the reaction of substituted pyrrole [C4H 4N(CH2NMe2)-2] with 1 equiv of phenyl isocyanate in diethyl ether yields a pyrrolyl attached urea derivative {C 4H3N(CH2NMe2)-2-[C(=O)NHPh]-1} (3). The demethanation reaction of AlMe3 with 1 equiv of 3 in methylene chloride at 0 °C afforded O-bounded and N-bounded aluminum dimethyl compounds {C4H3N(CH2-NMe 2)-2-[C(=O)NPh]-1}AlMe2 (4a) and {C4H 3N(CH2NMe2)-2-[CO(=NPh)]-1}AlMe2 (4b) in a total 78{\%} yield after recrystallization. Both 4a and 4b are observed in 1H NMR spectra; however, the relative ratio of 4a and 4b depends on the solvent used. Two equivalents of AlMe3 was reacted with 3 in methylene chloride to yield a dinuclear aluminum compound AlMe 3{C4H3N(CH2NMe 2)-2-[C(=O)NPh]-1}AlMe2 (5). Reaction of 5 with another equivalent of ligand 3 results in the re-formation of compounds 4a and 4b.",
author = "Tsai, {Chia Fu} and Chen, {Hsing Jen} and Chang, {Jr Chiuan} and Hung, {Cheng Hsiang} and Lai, {Chun Chia} and Hu, {Ching Han} and Huang, {Jui Hsien}",
year = "2004",
month = "3",
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language = "English",
volume = "43",
pages = "2183--2188",
journal = "Inorganic Chemistry",
issn = "0020-1669",
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Metal-Induced Coordination Inversion and Carbon-Nitrogen Bond Rearrangement. Structurally Characterized Phenyl Isocyanate Inserted into Aluminum Methyl Compounds and O- and N-Bound Aluminum Compounds. / Tsai, Chia Fu; Chen, Hsing Jen; Chang, Jr Chiuan; Hung, Cheng Hsiang; Lai, Chun Chia; Hu, Ching Han; Huang, Jui Hsien.

In: Inorganic Chemistry, Vol. 43, No. 6, 22.03.2004, p. 2183-2188.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Metal-Induced Coordination Inversion and Carbon-Nitrogen Bond Rearrangement. Structurally Characterized Phenyl Isocyanate Inserted into Aluminum Methyl Compounds and O- and N-Bound Aluminum Compounds

AU - Tsai, Chia Fu

AU - Chen, Hsing Jen

AU - Chang, Jr Chiuan

AU - Hung, Cheng Hsiang

AU - Lai, Chun Chia

AU - Hu, Ching Han

AU - Huang, Jui Hsien

PY - 2004/3/22

Y1 - 2004/3/22

N2 - [C4H3N(CH2NMe2)-2]AlMe 2 (1) is prepared in 88% yield by the reaction of substituted pyrrole [C4H4N(CH2NMe2)-2] with 1 equiv of AlMe3 in methylene chloride. Reaction of compound 1 with 1 equiv of phenyl isocyanate in toluene generates a seven-membered cycloaluminum compound {C4H3N[CH2NPh(CONMe 2)]-2}AlMe2 (2). The phenyl isocyanate was inserted into the aluminum and dimethylamino nitrogen bond and induced an unusual rearrangement which results in C-N bond breaking and formation. A control experiment shows that the reaction of substituted pyrrole [C4H 4N(CH2NMe2)-2] with 1 equiv of phenyl isocyanate in diethyl ether yields a pyrrolyl attached urea derivative {C 4H3N(CH2NMe2)-2-[C(=O)NHPh]-1} (3). The demethanation reaction of AlMe3 with 1 equiv of 3 in methylene chloride at 0 °C afforded O-bounded and N-bounded aluminum dimethyl compounds {C4H3N(CH2-NMe 2)-2-[C(=O)NPh]-1}AlMe2 (4a) and {C4H 3N(CH2NMe2)-2-[CO(=NPh)]-1}AlMe2 (4b) in a total 78% yield after recrystallization. Both 4a and 4b are observed in 1H NMR spectra; however, the relative ratio of 4a and 4b depends on the solvent used. Two equivalents of AlMe3 was reacted with 3 in methylene chloride to yield a dinuclear aluminum compound AlMe 3{C4H3N(CH2NMe 2)-2-[C(=O)NPh]-1}AlMe2 (5). Reaction of 5 with another equivalent of ligand 3 results in the re-formation of compounds 4a and 4b.

AB - [C4H3N(CH2NMe2)-2]AlMe 2 (1) is prepared in 88% yield by the reaction of substituted pyrrole [C4H4N(CH2NMe2)-2] with 1 equiv of AlMe3 in methylene chloride. Reaction of compound 1 with 1 equiv of phenyl isocyanate in toluene generates a seven-membered cycloaluminum compound {C4H3N[CH2NPh(CONMe 2)]-2}AlMe2 (2). The phenyl isocyanate was inserted into the aluminum and dimethylamino nitrogen bond and induced an unusual rearrangement which results in C-N bond breaking and formation. A control experiment shows that the reaction of substituted pyrrole [C4H 4N(CH2NMe2)-2] with 1 equiv of phenyl isocyanate in diethyl ether yields a pyrrolyl attached urea derivative {C 4H3N(CH2NMe2)-2-[C(=O)NHPh]-1} (3). The demethanation reaction of AlMe3 with 1 equiv of 3 in methylene chloride at 0 °C afforded O-bounded and N-bounded aluminum dimethyl compounds {C4H3N(CH2-NMe 2)-2-[C(=O)NPh]-1}AlMe2 (4a) and {C4H 3N(CH2NMe2)-2-[CO(=NPh)]-1}AlMe2 (4b) in a total 78% yield after recrystallization. Both 4a and 4b are observed in 1H NMR spectra; however, the relative ratio of 4a and 4b depends on the solvent used. Two equivalents of AlMe3 was reacted with 3 in methylene chloride to yield a dinuclear aluminum compound AlMe 3{C4H3N(CH2NMe 2)-2-[C(=O)NPh]-1}AlMe2 (5). Reaction of 5 with another equivalent of ligand 3 results in the re-formation of compounds 4a and 4b.

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