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]
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.J.C.S. acknowledges the NRF (Grant 2054243) and the UFS
for financial support. Financial support from Syngaschem BV,
The Netherlands, and the UFS is also gratefully acknowledged
(B.E.B., E.E., and J.C.S.).http://pubs.rsc.org/en/journals/journalissues/ic2017-03-31hb2016Chemistr
