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Juxtaposition of the strong back-bonding carbonyl ligand and weak back-bonding acetonitrile ligand in binuclear iron complexes

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Abstract

The binuclear iron complexes (CH3CN)2Fe2(CO) n (n = 7, 6), containing both the strongly back-bonding CO ligand and the weakly back-bonding acetonitrile ligand, have been investigated by density functional theory. The acetonitrile ligands are always found to be terminal in such structures. Heptacarbonyl structures are found at similar energies, with both acetonitrile ligands bonded to the same iron atom or with each acetonitrile ligand bonded to a different iron atom. Various combinations of bridging and semibridging CO groups are found in these (CH3CN)2Fe2(CO)7 structures approaching triply (bridged + semibridged) structures for the structures with symmetrically distributed acetonitrile ligands. The latter structures thus resemble the well-established triply bridged structure for the related binary iron carbonyl Fe2(CO)9. For the hexacarbonyl (CH3CN)2Fe2(CO)6, both triplet unbridged structures and singlet doubly bridged structures are found. The triplet (CH3CN)2Fe2(CO)6 structures have slightly lower energies relative to the singlet structures.

Graphical abstract

The acetonitrile ligands in (CH3CN)2Fe2(CO) n (n = 7, 6) are always found to be terminal ligands. Various combinations of bridging and semibridging CO groups are found in these (CH3CN)2Fe2(CO)7 structures approaching triply (bridged + semibridged) structures for the structures with symmetrically distributed acetonitrile ligands. For the hexacarbonyl (CH3CN)2Fe2(CO)6, both triplet unbridged structures and singlet doubly bridged structures are found.

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Acknowledgments

The research in China was supported by the Guangdong Province Universities and Colleges Pearl River Scholar Funded Scheme (2012), the Research Fund for the Doctoral Program of Higher Education (20104407110007) and the National Natural Science Foundation of China (21273082). Research at the University of Georgia was supported by the US National Science Foundation (Grant CHE-1057466).

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Authors and Affiliations

  1. MOE Key Laboratory of Theoretical Chemistry of the Environment, Center for Computational Quantum Chemistry, South China Normal University, Guangzhou, 510631, People’s Republic of China

    Guoliang Li, Lihua Liu, Jing Wang, Qian-shu Li & R. Bruce King

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

    Yaoming Xie & R. Bruce King

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  1. Guoliang Li
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  2. Lihua Liu
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  3. Jing Wang
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  4. Qian-shu Li
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  5. Yaoming Xie
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Correspondence to Qian-shu Li or R. Bruce King.

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Li, G., Liu, L., Wang, J. et al. Juxtaposition of the strong back-bonding carbonyl ligand and weak back-bonding acetonitrile ligand in binuclear iron complexes. Transition Met Chem 38, 617–625 (2013). https://doi.org/10.1007/s11243-013-9729-1

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