Theoretical studies on the high-spin binuclear cyclopentadienyliron derivatives Cp₂Fe₂(CN)_n (Cp = η⁵-C₅H₅; n = 6, 5, 4, 3, 2, 1)

Abstract

Theoretical studies on the cyclopentadienyliron derivatives Cp₂Fe₂(CN)_n (Cp = η⁵-C₅H₅; n = 6, 5, 4, 3, 2, 1) indicate that high-spin species with terminal Cp rings and bridging cyanide ligands up to a maximum of two bridges are predicted to be the lowest energy structures, which are paramagnetic complexes. Cp₂Fe₂(CN)₃ and Cp₂Fe₂(CN)₂ appear to be relatively stable with respect to dissociation of a cyanide ligand, while the binuclear derivatives Cp₂Fe₂(CN)_n (n = 6, 5, 4, 3) are all more stable than the mononuclear fragments.

Keywords:

• density functional theory
• high spin
• cyclopentadienyliron derivatives
• cyanide ligand
• paramagnetic

Acknowledgements

The authors are indebted to Chinese National Natural Science Foundation (20903010, 21243008, 21373025 and 61201352), Beijing Municipal Natural Science Foundation (2132035), 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, and National Basic Research Program of China (973 Program) (No. 2013CB329606) for support of this research.