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Molecular orbital interpretation of the metal–metal multiple bonding in coaxial dibenzene dimetal compounds of iron, manganese, and chromium

  • Hui Wang
  • Dong Die
  • Hongyan Wang
  • Yaoming Xie
  • R. Bruce King
  • Henry F. SchaeferIII
Regular Article
Part of the following topical collections:
  1. Dunning Festschrift Collection

Abstract

Both coaxial and perpendicular singlet spin state structures are found for the dibenzene dimetal complexes (C6H6)2M2 (M = Fe, Mn, and Cr) using density functional theory. For (C6H6)2M2 (M = Fe, Mn), the coaxial structure is the lower energy structure, whereas for (C6H6)2Cr2 the perpendicular structure is the lower energy structure. These coaxial structures are predicted to have very short M–M distances of ~1.98 Å for (C6H6)2Fe2, ~1.75 Å for (C6H6)2Mn2, and ~1.68 Å for (C6H6)2Cr2. Investigation into the frontier molecular orbitals suggests a formal 2π Fe=Fe double bond in (C6H6)2Fe2, a σ + 2π Mn≡Mn triple bond in (C6H6)2Mn2, and a σ + 2π + δ quadruple bond in (C6H6)2Cr2. This gives each metal atom in these coaxial (C6H6)2M2 (M = Fe, Mn, Cr) derivatives a 16-electron configuration suggesting an 8-orbital d 5 p 3 metal valence orbital manifold without the involvement of the s orbital. The coaxial (C6H6)2M2 (M = Fe, Mn) derivatives have ideal sixfold D 6h symmetry. However, distortion of coaxial (C6H6)2Cr2 from D 6h symmetry to D 2h symmetry is observed because of involvement of only one orbital from the {d(xy), d(x 2 − y 2)} set of δ symmetry of each chromium atom in the Open image in new window formal quadruple bond.

Keywords

Dibenzene dimetal compounds Metal–metal multiple bonding Molecular orbitals Density functional theory 

Notes

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 also 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 U.S. National Science Foundation (Grants CHE-1057466 and CHE-1054286).

Supplementary material

214_2014_1459_MOESM1_ESM.pdf (178 kb)
Supplementary material 1 (PDF 177 kb)

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Copyright information

© Springer-Verlag Berlin Heidelberg 2014

Authors and Affiliations

  1. 1.School of Physical Science and TechnologySouthwest Jiaotong UniversityChengduChina
  2. 2.Research Center for Advanced Computation, School of Physics and ChemistryXihua UniversityChengduChina
  3. 3.Department of Chemistry and the Center for Computational Quantum ChemistryUniversity of GeorgiaAthensUSA

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