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The hapticity of octafluorocyclooctatetraene in its first-row mononuclear transition metal carbonyl complexes: effect of perfluorination

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Abstract

The iron tricarbonyl complex of octafluorocyclooctatetraene was synthesized by Hughes and co-workers and shown by X-ray crystallography to have a trihapto–monohapto structure (η3,1-C8F8)Fe(CO)3 in contrast to the tetrahapto structure (η4-C8H8)Fe(CO)3 formed by the non-fluorinated cyclooctatetraene. This difference has stimulated a comprehensive density functional theoretical study of the octafluorocyclooctatetraene metal carbonyl complexes (C8F8)M(CO) n (n = 4, 3, 2, 1 for M = Ti, V, Cr, Mn, and Fe; n = 3, 2, 1 for M = Co, Ni) for comparison with their hydrogen analogues (C8H8)M(CO) n . In most such systems, the substitution of fluorine for hydrogen leads to relatively small changes in the preferred structures. However, for the iron carbonyl derivatives (C8X8)Fe(CO)3 (X = H, F), the difference observed experimentally has been confirmed by theory with (η3,1-C8F8)Fe(CO)3 and (η4-C8H8)Fe(CO)3 being the lowest energy structures by 4 and 14 kcal/mol, respectively. The ligand exchange reactions C8H8 + (C8F8)M(CO) n  → C8F8 + (C8H8)M(CO) n are predicted to be exothermic for almost all of the systems considered, with the (η3,1-C8X8)Fe(CO)3 system being the main exception. This suggests that the C8F8 ligand generally bonds more weakly to transition metals than the C8H8 ligand in accord with the electron-withdrawing effect of the ligand fluorine atoms.

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Acknowledgments

We are grateful for financial support from the China Scholarship Council and hospitality of Center for Computational Quantum Chemistry of the University of Georgia, USA. We acknowledge financial support from the Fundamental Research Funds for the Central Universities (Grant SWJTU12CX084), the China National Science Foundation (Grant 11174237), the Sichuan Province, Applied Science and Technology Project (Grant 2013JY0035), the open research fund of the Key Laboratory of Advanced Scientific Computation, Xihua University (Grant: szjj2012-035), and the US National Science Foundation (Grant CHE-1057466).

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Authors and Affiliations

  1. School of Physical Science and Technology, Southwest Jiaotong University, Chengdu, 610031, China

    Hui Wang & Hongyan Wang

  2. School of Physics and Chemistry, Research Center for Advanced Computation, Xihua University, Chengdu, 610039, China

    Dong Die

  3. Department of Chemistry and Center for Computational Quantum Chemistry, University of Georgia, Athens, GA, 30602, USA

    R. Bruce King

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  1. Hui Wang
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  2. Hongyan Wang
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  3. Dong Die
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Correspondence to Hongyan Wang or R. Bruce King.

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Wang, H., Wang, H., Die, D. et al. The hapticity of octafluorocyclooctatetraene in its first-row mononuclear transition metal carbonyl complexes: effect of perfluorination. Transition Met Chem 39, 95–109 (2014). https://doi.org/10.1007/s11243-013-9778-5

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