Buitendach, Blenerhassitt E.Erasmus, ElizabethLandman, MarileNiemantsverdriet, J. W. (Hans)Swarts, Jannie C.2016-09-212016-03Buitendach, BE, Erasmus, E, Landman, M, Niemantsverdriet, JWH & Swarts, JC 2016, '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]', Inorganic Chemistry, vol. 55, no. 5, pp. 1992-2000.0260-1818 (print)1460-4760 (online)10.1021/acs.inorgchem.5b02250http://hdl.handle.net/2263/56776Reaction 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.en© 2016 American Chemical SocietyManganeseFerroceneBetadiketonato complexesSubstituent effectsElectronic spectraX-ray photoelectron spectroscopyBinding energy predictionsPostprint Article