Can Electrochemical Measurements Be Used To Predict X-ray Photoelectron Spectroscopic Data? The Case of Ferrocenyl-β-Diketonato Complexes of Manganese(III)

Inorganic Chemistry
Blenerhassitt E BuitendachJannie C Swarts

Abstract

In order to better understand intramolecular communication between molecular fragments, a series of ferrocene-functionalized β-diketonato manganese(III) complexes, [Mn(FcCOCHCOR)3] with R = CF3, 1, CH3, 2, Ph = C6H5, 3, and Fc = FeII(η5-C5H4)(η5-C5H5), 4, the mixed ligand β-diketonato complex [Mn(FcCOCHCOFc)2(FcCOCHCOCH3)], 5, as well as the acac complex [Mn(CH3COCHCOCH3)3], 6, were subjected to an electrochemical and X-ray photoelectron spectroscopy (XPS) study. The ferrocenyl (FeII) and MnIII redox potentials, E°', and photoelectron lines were sufficiently resolved in each complex to demonstrate a linear correlation between E°' and group electronegativities of ligand R groups, χR, or ΣχR, as well as with binding energies of both the Fe 2p3/2 and Mn 2p3/2 photoelectron lines. These relationships are consistent with effective communication between molecular fragments of 1-5. From these relationships, prediction of Mn and Fe core electron binding energies in [Mn(R1COCHCOR2)3] complexes from known manganese and/or ferrocenyl redox potentials are, therefore, now possible. Ligand infrared carbonyl stretching frequencies were successfully related to binding energy as a measure of the energy required for inner-sphere reorganization. ...Continue Reading

References

May 15, 2002·Inorganic Chemistry·Jasmine R BryantJames M Mayer
Mar 23, 2006·Journal of the American Chemical Society·Frédéric Barrière, William E Geiger
Jun 17, 2008·Journal of Hazardous Materials·M B TalawarA Subhananda Rao
Mar 27, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Michael J CookJannie C Swarts
May 23, 2009·Journal of the American Chemical Society·Fabian SpänigAndreas Hirsch
Jan 16, 2010·Bioorganic & Medicinal Chemistry Letters·Ingo OttRainer F Winter
Oct 30, 2016·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Blenerhassitt E BuitendachJannie C Swarts

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