title: 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.
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 2p3/2and Fe 2p3/2core-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 2p3/2envelope 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 representingfacand the more stablemerisomers respectively. Stronger electron-donating ligands stabilizefacmore thanmerisomers. 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 2p3/2photoelectron lines, the ratio of satellite to main peak intensities, and the degree of covalence of the Mn-O bond.
authors: Department of Chemistry, University of the Free State, Bloemfontein 9300, South Africa. blenerbuitendach@gmail.com.
authors: Blenerhassitt E
authors: BE
authors: Buitendach
authors: Department of Chemistry, University of the Free State, Bloemfontein 9300, South Africa. ErasmusE@ufs.ac.za.
authors: Elizabeth
authors: E
authors: Erasmus
authors: SynCat@DIFFER, Syngaschem BV, De Zaale 20, Eindhoven 5612 AJ, The Netherlands. j.w.niemantsverdriet@tue.nl.
authors: J W Hans
authors: JW
authors: Niemantsverdriet
authors: Department of Chemistry, University of the Free State, Bloemfontein 9300, South Africa. swartsjc@ufs.ac.za.
authors: Jannie C
authors: JC
authors: Swarts
mesh_terms: D004563:Electrochemistry; D005296:Ferrous Compounds / Q000737:chemistry*; D008345:Manganese / Q000737:chemistry*; D000075163:Metallocenes; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D056951:Photoelectron Spectroscopy
chemical_list: D005296:Ferrous Compounds; D000075163:Metallocenes; D009942:Organometallic Compounds; D008345:Manganese; C004998:ferrocene
keywords: X-ray photoelectron spectroscopy; charge transfer; ferrocene; manganese; multiplet splitting; β-diketonato complexes