A density functional theory study of paramagnetic cyclopentadienylcobalt(III) derivatives: fluoride versus cyanide

Original Paper
Part of the following topical collections:
  1. Topical Collection on the occasion of Prof. Tim Clark’s 65th birthday


The cobalt(III) complexes Cp2Co2F4 and Cp2Co2(CN)4 have been studied by density functional theory methods as representatives of the experimentally known Cp2Co2X4 species with the weak-field fluoride ligand and the strong-field cyanide ligand. Both complexes were found to have relatively complicated energy surfaces with low-energy triplet and quintet spin state structures as well as the expected singlet-state structures for Co(III) complexes. This existence of singlet-, triplet-, and quintet-state structures of similar energies complicates the study of these complexes by density functional theory. The B3LYP* method of Reiher et al. was chosen in an effort to provide the most reliable estimates of the relative energies of the singlet, triplet, and quintet spin states. The lowest-energy Cp2Co2F4 structure was found to be a doubly bridged quintet spin state structure, with similar triplet and singlet structures lying within ∼4 kcal mol−1 of this quintet structure. The lowest-energy Cp2Co2(CN)4 structure was found to be a triplet spin state structure, with a singlet structure lying within ∼1 kcal mol−1 of this triplet structure. Almost all of the Cp2Co2X4 structures were found to have nonbonding Co···Co distances in excess of 2.9 Å, as expected for Co(III) complexes. In general, structures with trans stereochemistry of the Cp and other terminal ligands were found to be of lower energy than the corresponding structures with cis stereochemistry.


Cyclopentadienylmetal halides Cobalt Cyanide Fluoride Paramagnetic molecules Metal–metal interactions Density functional theory 



The authors are indebted to the Chinese National Natural Science Foundation (20903010, 21243008, 21373025), the Beijing Municipal Natural Science Foundation (2132035), the Opening Project of State Key Laboratory of Explosion Science of Technology (Beijing Institute of Technology) (2DkT10-01a and ZDKT12-03), Excellent Young Scholars Research Fund of Beijing Institute of Technology, (2012YG0202), Beijing Higher Education Young Elite Teacher Project (YETP1226) and the U.S. National Science Foundation (grants CHE-1057466 and CHE-1054286) for their support of this research.

Supplementary material

894_2014_2153_MOESM1_ESM.pdf (636 kb)
Supporting Information Tables S1 to S8: Coordinates of the singlet, triplet, and quintet spin state structures of Cp2Co2F4; Tables S9 to S20: Coordinates of the singlet, triplet, and quintet spin state structures of Cp2Co2(CN)4; Tables S21 to S28: Harmonic vibrational frequencies of the singlet, triplet, and quintet spin state structures of Cp2Co2F4; Tables S29 to S40: Harmonic vibrational frequencies of the singlet, triplet, and quintet spin state structures of Cp2Co2(CN)4; Figures S1 and S2: Optimized structures for the the singlet, triplet, and quintet states of Cp2Co2F4 and Cp2Co2(CN)4 using the B3LYP and BP86 methods; Tables S41 and S42: Total energies (E, in hartrees), relative energies (ΔE, in kcal mol−1), number of imaginary vibrational frequencies (Nimag), Co–Co bond distances (Å), and spin contamination <S 2> for the Cp2Co2F4 and Cp2Co2(CN)4 structures using the B3LYP and BP86 methods. (PDF 635  kb)


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Copyright information

© Springer-Verlag Berlin Heidelberg 2014

Authors and Affiliations

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

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