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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[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
Issue number6
Publication statusPublished - 2004 Mar 22


All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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