Kohlenwasserstoffverbrückte Metallkomplexe. XLIX Koordinationschemie von bis(ferrocenyl)substituierten 1,3-Diketonaten mit Ruthenium, Rhodium, Iridium und Palladium

Woisetschläger, Oliver E.; Geisbauer, Andreas; Polborn, Kurt; Beck, Wolfgang

doi:10.1002/(sici)1521-3749(200003)626:3<766::aid-zaac766>3.0.co;2-h

Cited by 14 publications

(5 citation statements)

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“…IR spectra of 3a–3d and 4 displayed the characteristic strong ν CO vibrations found between 1498 and 1572 cm –1 (Experimental Section), which is typical for chelate-bonded β-diketonato ligands in transition metal chemistry . A shift to lower wavenumbers is observed for 3a–3d and 4 compared to those of free β-diketones 2a–2d (1620–1710 cm –1 ), which allows the reaction progress to be monitored.…”

Section: Resultsmentioning

confidence: 91%

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: Resultsmentioning

confidence: 91%

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 IR spectra of 1 – 6 showed the characteristic strong ν (C=O) vibrations found between 1510–1562 cm −1 (Materials and Methods section) which is typical for chelate-bonded β-diketonato ligands in transition metal complexes [38,39]. Generally, a shift to lower wave numbers is observed for 1 – 6 compared to the free β -diketones 7 – 12 [40,41], which allows monitoring of the reaction progress.…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Spectroscopy and Electrochemistry in Relation to DFT Computed Energies of Ferrocene- and Ruthenocene-Containing β-Diketonato Iridium(III) Heteroleptic Complexes. Structure of [(2-Pyridylphenyl)2Ir(RcCOCHCOCH3]

et al. 2019

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A series of new ferrocene- and ruthenocene-containing iridium(III) heteroleptic complexes of the type [(ppy)2Ir(RCOCHCOR′)], with ppy = 2-pyridylphenyl, R = Fc = FeII(η5-C5H4)(η5-C5H5) and R′ = CH3 (1) or Fc (2), as well as R = Rc = RuII(η5-C5H4)(η5-C5H5) and R′ = CH3 (3), Rc (4) or Fc (5) was synthesized via the reaction of appropriate metallocene-containing β-diketonato ligands with [(ppy)2(μ-Cl)Ir]2. The single crystal structure of 3 (monoclinic, P21/n, Z = 4) is described. Complexes 1–5 absorb light strongly in the region 280−480 nm the metallocenyl β-diketonato substituents quench phosphorescence in 1–5. Cyclic and square wave voltammetric studies in CH2Cl2/[N(nBu)4][B(C6F5)4] allowed observation of a reversible IrIII/IV redox couple as well as well-resolved ferrocenyl (Fc) and ruthenocenyl (Rc) one-electron transfer steps in 1−5. The sequence of redox events is in the order Fc oxidation, then IrIII oxidation and finally ruthenocene oxidation, all in one-electron transfer steps. Generation of IrIV quenched phosphorescence in 6, [(ppy)2Ir(H3CCOCHCOCH3)]. This study made it possible to predict the IrIII/IV formal reduction potential from Gordy scale group electronegativities, χR and/or ΣχR′ of β-diketonato pendent side groups as well as from DFT-calculated energies of the highest occupied molecular orbital of the species involved in the IrIII/IV oxidation at a 98% accuracy level.

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“…The 1,3--diketones 1-ferrocenylbutane-1,3-dione (HL 1 ; Fc-COCH 2 COCH 3 ; Cain et al 1961;Hennig & Gurtler, 1968;Bell et al, 1992;Zakaria et al;1995) and 1,3-diferrocenylpropane-1,3-dione (HL 2 ; FcCOCH 2 COFc; Woisetschlager et al, 1999;du Plessis et al, 1998du Plessis et al, , 2001) form coordination (Zanello et al, 1998;Che et al, 1998;Li et al, 2002) and organometallic complexes of interest in catalysis (Abiko & Wang, 1996Cullen et al, 1991;Swarts et al, 1993;Woisetschlager et al, 2000;Vosloo et al, 2002;Conradie et al, 2005).…”

Section: Commentmentioning

confidence: 99%

Bis(1-ferrocenylbutane-1,3-dionato-κ²O,O′)copper(II) and bis(1,3-diferrocenylpropane-1,3-dionato-κ²O,O′)copper(II)

2006

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The title compounds, [CuFe2(C5H5)2(C9H8O2)2], (I), and [CuFe4(C5H5)4(C13H9O2)2], (II), are four-coordinate square-planar copper(II) complexes with two bidentate 1-ferrocenylbutane-1,3-dionate or 1,3-diferrocenylpropane-1,3-dionate ligands, respectively. The copper ion in (I) lies on an inversion centre, with one-half of the molecule in the asymmetric unit, while in (II), there are two independent half molecules in the asymmetric unit, with the copper ions also situated on inversion centres. The ferrocene substituents in (I) are in an anti arrangement. The molecules assemble in the crystal structure in layers with ferrocene groups at the surface. The pairs of ferrocene substituents on each ligand in complex (II) are syn and these adopt an anti arrangement with respect to the pair on the other diketonate ligand. As found in (I), complexes assemble in a layered structure with ferrocene-coated surfaces.

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Kohlenwasserstoffverbrückte Metallkomplexe. XLIX Koordinationschemie von bis(ferrocenyl)substituierten 1,3-Diketonaten mit Ruthenium, Rhodium, Iridium und Palladium

Cited by 14 publications

References 6 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]

Synthesis, Spectroscopy and Electrochemistry in Relation to DFT Computed Energies of Ferrocene- and Ruthenocene-Containing β-Diketonato Iridium(III) Heteroleptic Complexes. Structure of [(2-Pyridylphenyl)2Ir(RcCOCHCOCH3]

Bis(1-ferrocenylbutane-1,3-dionato-κ²O,O′)copper(II) and bis(1,3-diferrocenylpropane-1,3-dionato-κ²O,O′)copper(II)

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Kohlenwasserstoffverbrückte Metallkomplexe. XLIX Koordinationschemie von bis(ferrocenyl)substituierten 1,3-Diketonaten mit Ruthenium, Rhodium, Iridium und Palladium

Cited by 14 publications

References 6 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]

Synthesis, Spectroscopy and Electrochemistry in Relation to DFT Computed Energies of Ferrocene- and Ruthenocene-Containing β-Diketonato Iridium(III) Heteroleptic Complexes. Structure of [(2-Pyridylphenyl)2Ir(RcCOCHCOCH3]

Bis(1-ferrocenylbutane-1,3-dionato-κ2O,O′)copper(II) and bis(1,3-diferrocenylpropane-1,3-dionato-κ2O,O′)copper(II)

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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]

Bis(1-ferrocenylbutane-1,3-dionato-κ²O,O′)copper(II) and bis(1,3-diferrocenylpropane-1,3-dionato-κ²O,O′)copper(II)