Electrochemical Studies of Organometallic Complexes with Tetra-n-butylammonium Tetrakis[3,5-bis(trifluoromethyl)phenyl]borate as the Electrolyte. X-ray Crystal Structure of [C5(CF3)(CH3)4]Fe(C5H5)

Paul G. Gassman, John R. Sowa, Michael G. Hill, Kent R Mann

Research output: Contribution to journalArticlepeer-review

51 Scopus citations

Abstract

The tetra-n-butylammonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (TBA+TFPB-) electrolyte/methylene chloride solvent system improves the electrochemical reversibility of pentamethylcyclopentadienyl (Cp*) ruthenocenes, Cp*RuCp' (Cp' = fluorenyl, indenyl, cyclopentadienyl (Cp), acetylcyclopentadienyl, pentachlorocyclopentadienyl), as indicated by ipc/ip,a ratios of 0.79-1.0 as determined by cyclic voltammetry. The quasi-reversible potentials (E°') of the Cp*RuCp' complexes and the complete series of group 9 Cp2M and Cp*2M complexes (M = Fe, Ru, Os) are also reported in TBA+TFPB_/CH2Cl2. In addition, a study of the E°' values of group 9 complexes containing the (trifluoromethyl)tetramethylcyclopentadienyl (Cp) ligand indicate that the Cp complexes are slightly (0.06-0.08 V per Cp) more difficult to oxidize than the cyclopentadienyl (Cp) derivatives. The structure of [C5(CF3)(CH3)4]Fe(C5H5) was determined at -101 °C by a single-crystal X-ray diffraction study. The structure shows eclipsed Cp and Cp rings, and the iron to Cp centroid distance (1.643 Å) is slightly shorter than the iron to Cp centroid distance (1.651 Å); otherwise, no extreme differences in the coordination of the Cp and Cp rings are noted. An infrared spectroelectrochemistry study of trans-[CpFe(CO)2]2 shows that it is electrochemically oxidized to trans-[CpFe(CO)2]2+ in TBA+TFPB-/CH2C12.

Original languageEnglish (US)
Pages (from-to)4879-4885
Number of pages7
JournalOrganometallics
Volume14
Issue number10
DOIs
StatePublished - Oct 1995

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