Transition Metal Chemistry

, Volume 38, Issue 6, pp 617–625 | Cite as

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.

Keywords

CH3CN Iron Atom Isocyanide Metal Carbonyl Wiberg Bond Index 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.
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Notes

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).

Supplementary material

11243_2013_9729_MOESM1_ESM.pdf (361 kb)
Supplementary material 1 (PDF 360 kb)

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Copyright information

© Springer Science+Business Media Dordrecht 2013

Authors and Affiliations

  1. 1.MOE Key Laboratory of Theoretical Chemistry of the Environment, Center for Computational Quantum ChemistrySouth China Normal UniversityGuangzhouPeople’s Republic of China
  2. 2.Department of Chemistry and Center for Computational ChemistryUniversity of GeorgiaAthensUSA

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