Next Article in Journal
A Combined Molecular Cloning and Mass Spectrometric Method to Identify, Characterize, and Design Frenatin Peptides from the Skin Secretion of Litoria infrafrenata
Previous Article in Journal
Molecular Mechanism of the Flavonoid Natural Product Dryocrassin ABBA against Staphylococcus aureus Sortase A
Article Menu
Issue 11 (November) cover image

Export Article

Open AccessArticle
Molecules 2016, 21(11), 1427; doi:10.3390/molecules21111427

Properties of Manganese(III) Ferrocenyl-β-Diketonato Complexes Revealed by Charge Transfer and Multiplet Splitting in the Mn 2p and Fe 2p X-Ray Photoelectron Envelopes

1
Department of Chemistry, University of the Free State, Bloemfontein 9300, South Africa
2
SynCat@DIFFER, Syngaschem BV, De Zaale 20, Eindhoven 5612 AJ, The Netherlands
*
Author to whom correspondence should be addressed.
Academic Editor: Jeremy M. Rawson
Received: 9 September 2016 / Revised: 14 October 2016 / Accepted: 19 October 2016 / Published: 26 October 2016
(This article belongs to the Section Organometallic Chemistry)
View Full-Text   |   Download PDF [2540 KB, uploaded 26 October 2016]   |  

Abstract

A series of ferrocenyl-functionalized β-diketonato manganese(III) complexes, [Mn(FcCOCHCOR)3] with R = CF3, CH3, Ph (phenyl) and Fc (ferrocenyl) was subjected to a systematic XPS study of the Mn 2p3/2 and Fe 2p3/2 core-level photoelectron lines and their satellite structures. A charge-transfer process from the β-diketonato ligand to the Mn(III) metal center is responsible for the prominent shake-up satellite peaks of the Mn 2p photoelectron lines and the shake-down satellite peaks of the Fe 2p photoelectron lines. Multiplet splitting simulations of the photoelectron lines of the Mn(III) center of [Mn(FcCOCHCOR)3] resemble the calculated Mn 2p3/2 envelope of Mn3+ ions well, indicating the Mn(III) centers are in the high spin state. XPS spectra of complexes with unsymmetrical β-diketonato ligands (i.e., R not Fc) were described with two sets of multiplet splitting peaks representing fac and the more stable mer isomers respectively. Stronger electron-donating ligands stabilize fac more than mer isomers. The sum of group electronegativities, ΣχR, of the β-diketonato pendant side groups influences the binding energies of the multiplet splitting and charge transfer peaks in both Mn and Fe 2p3/2 photoelectron lines, the ratio of satellite to main peak intensities, and the degree of covalence of the Mn–O bond. View Full-Text
Keywords: manganese; ferrocene; β-diketonato complexes; multiplet splitting; charge transfer; X-ray photoelectron spectroscopy manganese; ferrocene; β-diketonato complexes; multiplet splitting; charge transfer; X-ray photoelectron spectroscopy
Figures

This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

Scifeed alert for new publications

Never miss any articles matching your research from any publisher
  • Get alerts for new papers matching your research
  • Find out the new papers from selected authors
  • Updated daily for 49'000+ journals and 6000+ publishers
  • Define your Scifeed now

SciFeed Share & Cite This Article

MDPI and ACS Style

Buitendach, B.E.; Erasmus, E.; Niemantsverdriet, J.W.H.; Swarts, J.C. Properties of Manganese(III) Ferrocenyl-β-Diketonato Complexes Revealed by Charge Transfer and Multiplet Splitting in the Mn 2p and Fe 2p X-Ray Photoelectron Envelopes. Molecules 2016, 21, 1427.

Show more citation formats Show less citations formats

Note that from the first issue of 2016, MDPI journals use article numbers instead of page numbers. See further details here.

Related Articles

Article Metrics

Article Access Statistics

1

Comments

[Return to top]

Molecules EISSN 1420-3049 Published by MDPI AG, Basel, Switzerland RSS E-Mail Table of Contents Alert
Back to Top