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Synthesis and Characterization of Stable Hypervalent Carbon Compounds (10-C-5) Bearing a 2,6-Bis(p-substituted phenyloxymethyl)benzene Ligand

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Contribution from the Department of Chemistry, Graduate School of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima 739-8526, Japan, Advanced Research Center for Science and Engineering, Waseda University, 3-4-1 Ohkubo, Shinjuku-ku, Tokyo 165-8555, Japan, Department of Applied Physics and Chemistry, The University of Electro-Communications, 1-5-1 Chofugaoka, Chofu, Tokyo 182-8585, Japan, and Department of Theoretical Molecular Science, Institute for Molecular Science, Myodaiji, Okazaki 444-8585, Japan
Cite this: J. Am. Chem. Soc. 2005, 127, 16, 5893–5901
Publication Date (Web):April 2, 2005
Copyright © 2005 American Chemical Society

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    X-ray analysis of bis(p-fluorophenyl)methyl cation bearing a 2,6-bis(p-tolyloxymethyl)benzene ligand showed a symmetrical structure (10-C-5) where the two C−O distances are identical, although the distance (2.690(4) Å) is longer than those (2.43(1) and 2.45(1) Å) of 1,8-dimethoxy-9-dimethoxymethylanthracene monocation, which was recently reported by us. However, X-ray analysis of the more stable aromatic xanthylium cation with the same benzene ligand showed the tetracoordinate carbon structure where only one of the two oxygen ligands is coordinated with the central carbon atom. These results clearly indicate that the carbocations (10-C-5) bearing the sterically flexible benzene ligand were quite sensitive to the electronic effect on the central carbon atom. The electron distribution analysis by accurate X-ray measurements and the density functional calculation on the initially mentioned bis(p-fluorophenyl)methyl cation clearly show that the central carbon atom and the two oxygen atoms are bonded even if the bond is weak and ionic based on the small value of the electron density (ρ(r)) and the small positive Laplacian value (∇2ρ(r)) at the bond critical points.

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     Waseda University.

     Hiroshima University.


     The University of Electro-Communications.

     Institute for Molecular Science.

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