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Synthesis, Molecular Structure and Properties of a Ferrocene-Based Difluoropyrrolo-Oxaborole Derivative

DOI: 10.1002/ejic.201402752 DOI Help

Authors: Andrew C. Benniston (Newcastle University) , Dumitru Sirbu (Academy of Sciences of Moldova) , Constantin Turta (Academy of Sciences of Moldova) , Michael R. Probert (Newcastle University) , William Clegg (Newcastle University)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: European Journal Of Inorganic Chemistry , PAGES 6212-6219

State: Published (Approved)
Published: December 2014
Diamond Proposal Number(s): 6749

Abstract: Reaction of 1,1-ferrocenedicarbonyl chloride with 3-ethyl-2,4-dimethylpyrrole in DCM produced the half-way product, namely, the ferrocene bis(2-ketopyrrole) derivative 2 and not the expected bis(dipyrromethene) compound. The 2-ketopyrrole compound readily reacted with BF3·Et2O to produce the bis(difluoropyrrolo)-oxaborole compound, FBF, as a red/brown solid which was characterised by X-ray crystallography. 57Fe Mössbauer spectra for 2 and FBF were consistent with low-spin iron(II) (d6) ferrocene derivatives. A cyclic voltammogram for 2 in acetonitrile revealed a reversible wave at +0.31 V vs. Fc+/Fc (ferrocene-based) and an irreversible wave at –2.38 V vs. Fc+/Fc (ketopyrrole-based). The electrochemical behaviour is severely perturbed by the chelation of the BF2 groups. Alterations to the electronic properties of 2 by formation of FBF are also evident in the absorption profiles. DFT calculations [B3PW91, 6-31G(3df)] support the observed changes in the electrochemistry findings and the Mössbauer spectroscopic data.

Subject Areas: Chemistry

Instruments: I19-Small Molecule Single Crystal Diffraction

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