title: Consequences of Electron-Density Manipulations on the X-ray Photoelectron Spectroscopic Properties of Ferrocenyl-β-diketonato Complexes of Manganese(III). Structure of [Mn(FcCOCHCOCH3)3].
abstract: Reaction of [Mn3(OAc)6O·3H2O](+) (1) with ferrocenyl β-diketones of the type FcCOCH2COR with R = CF3 (2a) and CH3 (2b), Ph = C6H5 (2c), and Fc = Fe(II)(η(5)-C5H4)(η(5)-C5H5) (2d) yielded a series of ferrocene-functionalized β-diketonato manganese(III) complexes 3a-3d, respectively, of general formula [Mn(FcCOCHCOR)3]. The mixed-ligand β-diketonato complex [Mn(FcCOCHCOFc)2(FcCOCHCOCH3)] (4) was obtained by reacting mixtures of diketones 2b and 2d with 1. A single-crystal X-ray structure determination of 3b (Z = 2, triclinic, space group P1̅) highlighted a weak axial elongating Jahn-Teller effect and a high degree of bond conjugation. An X-ray photoelectron spectroscopic study, by virtue of linear relationships between group electronegativities of ligand R groups, χR, or ∑χR, and binding energies of both the Fe 2p3/2 and Mn 2p3/2 photoelectron lines, confirmed communication between molecular fragments of 2a-2d as well as 3a-3d. This unprecedented observation allows prediction of binding energies from known β-diketonato side group χR values.
authors.affiliation: Department of Chemistry, University of the Free State , Bloemfontein 9300, South Africa.
authors.forename: Blenerhassitt E
authors.initials: BE
authors.lastname: Buitendach
authors.affiliation: Department of Chemistry, University of the Free State , Bloemfontein 9300, South Africa.
authors.forename: Elizabeth
authors.initials: E
authors.lastname: Erasmus
authors.affiliation: Department of Chemistry, University of Pretoria , Pretoria, South Africa.
authors.forename: Marilé
authors.initials: M
authors.lastname: Landman
authors.affiliation: Syngaschem BV, Helix Building, Campus of the Eindhoven University of Technology , Eindhoven, The Netherlands.
authors.forename: J W Hans
authors.initials: JW
authors.lastname: Niemantsverdriet
authors.affiliation: Department of Chemistry, University of the Free State , Bloemfontein 9300, South Africa.
authors.forename: Jannie C
authors.initials: JC
authors.lastname: Swarts