High energy photoelectron spectroscopy of transition metal complexes. Part 4.—Bis(arene) and related complexes of chromium, manganese and iron

Connor, Joseph A.; Derrick, L. M. R.; Hillier, Ian H.

doi:10.1039/f29747000941

Cited by 35 publications

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“…This broadening in fwhm compared to what was found for Fe can again be attributed to a combination of the high-spin state of the Mn(III) metal center and the presence of fac and mer conformations in the bulk [Mn(FcCOCHCOR) 3 ] material. The position of the binding energy of the Mn 2p 3/2 peaks at ∼641 eV is comparable to those found for Mn 0.25 Fe 0.75 Cr 2 O 4 (640.8 eV) and [Mn(CO) 3 (C 5 H 5 )] (640.6 eV) . Similar to that of the Fe 2p peaks, the binding energy of the Mn 2p peaks also increases with an increase in the R group χ R (Figures and and Table ).…”

Section: Resultssupporting

confidence: 79%

“…A full iron redox state change from Fe 2+ to Fe 3+ would, for example, represent a 1 eV binding energy change. The observed binding energy range is also in good agreement with published values for neat ferrocene (707.8 eV) 36 and for ferrocene on Ag(100) (707.9 eV), 37 but it is lower than the binding energy of a ferrocenyl linked via an aminoalkyl silane onto silicon (709.7 eV). 38 The only other photoelectron lines that could be detected in the XPS spectra of 2b−2d were carbon (∼284.8 eV) and oxygen (∼528.8 eV).…”

Section: Inorganic Chemistrymentioning

confidence: 99%

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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]

et al. 2016

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and 2d with 1. A single crystal X-ray structure determination of 3b (Z=2, triclinic, space group P-1) 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, χ R , or χ R , and binding energies of both the Fe 2p 3/2 and Mn 2p 3/2 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 χ R values.Keywords: Manganese, ferrocene, betadiketonato complexes, substituent effects, electronic spectra, X-ray photoelectron spectroscopy, binding energy predictions. IntroductionThe first row transition metal, manganese, exhibits a wide variety of oxidation states in compounds ranging from Mn(I), e. we then highlight intramolecular communication between molecular fragments of 3a-3d from results of an X-ray photoelectron spectroscopic (XPS) study. Results and discussion Synthesis and characterizationThe ferrocene-containing manganese ( IR spectra of 3a-3d and 4 displayed the characteristic strong ν CO vibrations found between 1498-1572 cm -1 (Experimental Part) which is typical for chelate-bonded β-diketonato ligands in transition metal chemistry. 22 A shift to lower wave numbers is observed for 3a-3d and 4 compared to the free β-diketones 2a-2d (1620 -1710 cm -1 ) 23 which allows the monitoring of the reaction progress. Prominent CH-stretching bands are also observed at ca. 3100 cm -1 .Peak maxima of the UV-Vis spectra of complexes 3a-3d and 4 ( Figure 1) are summarized in Table 1. Dichloromethane solutions of the highly soluble complexes 3a-3c and 4 all showed relatively high extinction coefficients. All complexes followed the Beer-Lambert law, A = εCl, which implies a linear relationship between absorbance and concentration. Van der Zeiden 24 reported a similar lower energy band in tungsten(0) -diketonato complexes and assigned it to a MLCT band with destabilized t 2g level after appropriate calculations. Single Crystal X-ray structure of 3bTo understand the trends observed in XPS-obtained binding energies for Fe(II) (and also Mn(III)) of complexes 3a -3d described in the next section, an evaluation of the structural characteristics of 3b is useful. The fac isomer of complex 3b crystallized from toluene in the triclinic space group P-1 having ca. 1 disordered solvent molecule for every two molecules of 3b. The refinement parameters and crystal data are summarized in Table 2 and the molecular structure of 3b, highlighting atom labeling, are shown in Figure 2. Selected bond distances and bond angles are summarized in the caption of Figure 2, but the full set of bond lengths and angles is available in Supplementary Information.

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Section: Resultssupporting

confidence: 79%

Section: Inorganic Chemistrymentioning

confidence: 99%

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]

et al. 2016

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“…The XPS experiment has been further analyzed to explain how the obtained signals clearly indicate the presence of three oxidation states of manganese ions. Moreover, the reported typical values of the three manganese oxidation states at the NIST database are consistent with the signals obtained for 1 as reported in the supplementary information [45][46][47][48][49][50][51][52][53][54][55][56][57][58].…”

Section: Infrared Spectroscopysupporting

confidence: 85%

Tetramer Compound of Manganese Ions with Mixed Valence [MnII MnIII MnIV] and Its Spatial, Electronic, Magnetic, and Theoretical Studies

et al. 2018

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Using different spectroscopic techniques and computational calculations, we describe the structural and electromagnetic relationship that causes many interesting phenomena within a novel coordination compound with mixed valence manganese (II, III and IV) in its crystal and powder state. The novel compound [MnII MnIII MnIV(HL)2(H2L)2(H2O)4](NO3)2(H2O) 1 was obtained with the Schiff base (E)-2-((2-hydroxybenzylidene)amine)-2-(hydroximethyl)propane-1,3-diol, (H4L), and Mn(NO3)2.4H2O. The coordination reaction was promoted by the deprotonation of the ligand by the soft base triethylamine. The paper’s main contribution is the integration of the experimental and computational studies to explain the interesting magnetic behavior that the mixed valence manganese multimetallic core shows. The results presented herein, which are rarely found for Mn(II), (III) and (IV) complexes, will contribute to the understanding of the magnetic communication generated by the valence electrons and its repercussion in the local geometry and in the overall crystalline structure.

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“…Also, this range of binding energies are larger than the binding energy range of 0.34 eV which was found for the Fe 2p 3/2 photoelectron lines of Mn(B-diketonato) 3 complexes. 28,29 The binding energies obtained for the Fe 2p 3/2 photoelectron lines of 1-7 correlates very well with other Fe(II) species, iron disphosphide, 30 bis(cyclopentadenyl)iron, 31 and the ferrocenylgroup in Mn(B-diketonato) 3 , 28,29 all located at ca. 707.7 eV.…”

Section: Resultsmentioning

confidence: 58%

Electronic effects of group fragments on the XPS of Fe 2p and 3p photoelectron lines of ferrocenyl-containing chalcones

Erasmus

2017

S.Afr.j.chem.

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A series of ferrocenyl-containing chalcones, Fc-CO-CH=CH-C 6 H 4 R, with the R-group on the para-position on the phenyl ring and R = OCH 3 (1), CH 3 (2), C 6 H 5 (3), tBu (4), H (5), Br (6) and CF 3 (7) were subjected to an X-ray photoelectron spectroscopy (XPS) study. The linear relationships obtained between the Gordy-scale group electronegativity of molecular fragment R, ÷ R , and the maximum binding energies of the Fe 2p 3/2 and the Fe 3p 3/2 photoelectron lines, confirmed communication between the iron atom of the ferrocene moiety and the molecular fragments, R, of 1-7. These relationships illustrated that the influence of the electronic properties of the molecular fragments are more pronounced in the Fe 3p photoelectron lines than in the Fe 2p photoelectron lines.

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High energy photoelectron spectroscopy of transition metal complexes. Part 4.—Bis(arene) and related complexes of chromium, manganese and iron

Cited by 35 publications

References 0 publications

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]

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]

Tetramer Compound of Manganese Ions with Mixed Valence [MnII MnIII MnIV] and Its Spatial, Electronic, Magnetic, and Theoretical Studies

Electronic effects of group fragments on the XPS of Fe 2p and 3p photoelectron lines of ferrocenyl-containing chalcones

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High energy photoelectron spectroscopy of transition metal complexes. Part 4.—Bis(arene) and related complexes of chromium, manganese and iron

Cited by 35 publications

References 0 publications

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]

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]

Tetramer Compound of Manganese Ions with Mixed Valence [MnII MnIII MnIV] and Its Spatial, Electronic, Magnetic, and Theoretical Studies

Electronic effects of group fragments on the XPS of Fe 2p and 3p photoelectron lines of ferrocenyl-containing chalcones

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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]

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]