Journal article

Authors list: Molski, MJ; Mollenhauer, D; Gohr, S; Paulus, B; Khanfar, MA; Shorafa, H; Strauss, SH; Seppelt, K

Publication year: 2012

Pages: 6644-6654

Journal: Chemistry - A European Journal

Volume number: 18

Issue number: 21

ISSN: 0947-6539

DOI Link: https://doi.org/10.1002/chem.201102960

Publisher: Wiley

Abstract: 

The halogenated benzenes C₆HF₅, 2,4,6‐C₆H₃F₃, 2,3,5,6‐C₆H₂F₄, C₆F₆, C₆Cl₆, C₆Br₆, and C₆I₆
were converted into their corresponding cation radicals by using
various strong oxidants. The cation‐radical salts were isolated and
characterized by electron paramagnetic resonance (EPR) spectroscopy and
by single‐crystal X‐ray diffraction. The thermal stability of the cation
radicals increased with decreasing hydrogen content. As expected, the
cation radicals [C₆HF₅]⁺ and 2,3,5,6‐[C₆H₂F₄]⁺ had structures with the same geometry as C₆HF₅ and 2,3,5,6‐[C₆H₂F₄]. In contrast, the cation radicals [C₆F₆]⁺, [C₆Cl₆]⁺, and possibly also [C₆Br₆]⁺ exhibited Jahn–Teller‐distorted geometries in the crystalline state. In the case of C₆F₆⁺Sb₂F₁₁⁻, two low‐symmetry geometries were observed in the same crystal. Interestingly, the structures of the cation radicals 2,4,6‐[C₆H₃F₃]⁺ and C₆I₆⁺
did not exhibit Jahn–Teller distortions. DFT calculations showed that
the explanation for the lack of distortion of these cations from the D_3h or D_6h symmetry of the neutral benzene precursor was different for 2,4,6‐[C₆H₃F₃]⁺ than for [C₆I₆]⁺.

Harvard Citation style: Molski, M., Mollenhauer, D., Gohr, S., Paulus, B., Khanfar, M., Shorafa, H., et al. (2012) Halogenated Benzene Cation Radicals, Chemistry - A European Journal, 18(21), pp. 6644-6654. https://doi.org/10.1002/chem.201102960

APA Citation style: Molski, M., Mollenhauer, D., Gohr, S., Paulus, B., Khanfar, M., Shorafa, H., Strauss, S., & Seppelt, K. (2012). Halogenated Benzene Cation Radicals. Chemistry - A European Journal. 18(21), 6644-6654. https://doi.org/10.1002/chem.201102960