The synthesis and molecular and crystal structures of 1-methyl-2-carboxy-1, 2-dicarba-closo-dodecaborane(12), 1-phenyl-2-carboxy-1,2-dicarba-closo- dodecaborane(12) and 1-phenyl-2-benzoyl-1,2-dicarba-closo-dodecaborane(12)

Ulaganathan Venkatasubramanian, David J. Donohoe, David Ellis, Barry T. Giles, Stuart A. MacGregor, Susan Robertson, Georgina M. Rosair, Alan J. Welch, Andrei S. Batsanov, Lynn A. Boyd, R. C B Copley, Mark A. Fox, J. A K Howard, Kenneth Wade

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Abstract

The structures of 1-Me-2-COOH-1,2-closo-C2B10H 10 (1), 1-Ph-2-COOH-1,2-closo-C2B10H 10 (2) and 1-Ph-2-COPh-1,2-closo-C2B10H 10 (3) have been determined by X-ray crystallography. In 1 the orientation of the COOH group is defined by ?COOH=65.0(2) syn°, and this group H-bonds to that in a second molecule via a centrosymmetric eight-membered ring, R22(8). DFT calculations on the parent species 1-COOH-1,2-closo-C2B 10H11 reveal that the structure with ? COOH=90syn°is preferred, with a barrier to COOH rotation of ˜17 kJmol-1. Similar calculations on 1 yield a lower rotational barrier, ˜7 kJmol-1, because internal H-bonding is now denied. In compound 2 the COOH group is twisted to lower ? values [5.0(3)°and 39.7(3)°] but both crystallographically independent molecules exist as dimers in the solid state by virtue of R22(8) rings. Compound 2 crystallises from wet solvent as a monohydrate, the structure of which reveals a non-planar centrosymmetric R 44(12) ring and near-orthogonal Ph and COOH substituents [?Ph=6.7(2) and ?COOH=78.0(2) syn°]. In compound 3 molecular association by H-bonding is blocked, so 3 serves as a useful comparative structure for 2. © 2003 Elsevier Ltd. All rights reserved.

Original languageEnglish
Pages (from-to)629-636
Number of pages8
JournalPolyhedron
Volume23
Issue number4
DOIs
Publication statusPublished - 12 Feb 2004

Keywords

  • Carborane
  • DFT calculations
  • Spectroscopy
  • X-ray crystallography

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    Venkatasubramanian, U., Donohoe, D. J., Ellis, D., Giles, B. T., MacGregor, S. A., Robertson, S., Rosair, G. M., Welch, A. J., Batsanov, A. S., Boyd, L. A., Copley, R. C. B., Fox, M. A., Howard, J. A. K., & Wade, K. (2004). The synthesis and molecular and crystal structures of 1-methyl-2-carboxy-1, 2-dicarba-closo-dodecaborane(12), 1-phenyl-2-carboxy-1,2-dicarba-closo- dodecaborane(12) and 1-phenyl-2-benzoyl-1,2-dicarba-closo-dodecaborane(12). Polyhedron, 23(4), 629-636. https://doi.org/10.1016/j.poly.2003.10.016