Europium and ytterbium complexes with <i>o</i>-iminoquinonato ligands: synthesis, structure, and magnetic behavior

Klementyeva, Svetlana V.; Lukoyanov, Anton N.; Afonin, M. Yu.; Mörtel, Max; Смоленцев, А. И.; Abramov, Pavel A.; Старикова, А. А.; Khusniyarov, Marat M.; Konchenko, Sergey N.

doi:10.1039/c8dt04849e

Cited by 21 publications

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References 116 publications

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“…The values of χ M T per complex of 24.5 and 32.6 emu K mol –1 (Figure ), measured at 297 K for 1-Eu 3 L 3 and 3-Eu 2 L 4 , respectively, are in agreement with the value calculated for three and four magnetically isolated 4f 7 ions [ L = 0, S = 7/2, 3χ M T (Eu II ) = 3 × 7.87 = 23.6 emu K mol –1 , and 4χ M T (Eu II ) = 4 × 7.87 = 31.5 emu K mol –1 ]. These values are also consistent with magnetic susceptibility values previously reported for mononuclear or polynuclear Eu(II) complexes …”

Section: Resultssupporting

confidence: 92%

“…In contrast the Eu(II) ions in the [Eu(Cl) 2 (bpm)(MeOH) 0.5 ] n polymer (bpm = 2,2′-bipyrimidine) are antiferromagnetically coupled ( J AF = −0.01 cm –1 ) . The χ M T versus T curve was reported to reach a maximum value at 2 K for the Eu(II) bpm polymers and at 3 K for the tetranuclear Eu(II) o -amidophenolate complex . In the case of 1-Eu 3 L 3 , the maximum value of χ M T is reached at a slightly higher temperature (6 K).…”

Section: Resultsmentioning

confidence: 97%

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Structure and Reactivity of Polynuclear Divalent Lanthanide Disiloxanediolate Complexes

et al. 2022

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Trinuclear molecular complexes of europium (II) and ytterbium(II) [Ln3{(Ph2SiO)2O}3(THF)6], 1-Ln 3 L 3 (Ln = Eu and Yb), supported by the dianionic tetraphenyl disiloxanediolate ligand, were synthesized via protonolysis of the [Ln{N(SiMe3)2}2(THF)2] complexes. In contrast, the reaction of [Sm{N(SiMe3)2}2(THF)2] with the (Ph2SiOH)2O ligand led to the isolation of the mixed-valent Sm(II)/Sm(III) complex [Sm3{(Ph2SiO)2O}3{N(SiMe3)2}(THF)4], 2-Sm 3 L 3 , which was crystallographically characterized. The Eu(II) complex 1-Eu 3 L 3 displays weak ferromagnetic coupling between the Eu(II) metal centers (J = 0.1035 cm–1). The addition of 3 equiv of (Ph2SiOK)2O to 1-Eu 3 L 3 resulted in the formation of the polynuclear Eu(II) dimer of dimers [K4Eu2{(Ph2SiO)2O}4(Et2O)2]2, 3-Eu 2 L 4 . Complexes 1-Ln 3 L 3 (Ln = Eu and Yb) are stable in solution at room temperature, while 3-Eu 2L4 shows higher reactivity and rapidly decomposes to give the mixed-valent Eu(II)/Eu(III) species [K3Eu2{(Ph2SiO)2O}4], 4-Eu 2 L 4 . Complex 1-Yb 3 L 3 affects the slow reductive disproportionation of carbon dioxide, but 1-Eu 3 L 3 does not display any reactivity toward CO2. However, the presence of one additional (Ph2SiO–)2O per Eu(II) metal center in 3-Eu 2 L 4 increases dramatically the reductive ability of the Eu(II) metal centers, affording the first example of carbon dioxide activation by an isolated divalent europium complex. The reduction of CO2 by 3-Eu 2 L 4 is immediate, and carbonate is formed selectively after the addition of a stoichiometric amount of CO2.

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Section: Resultssupporting

confidence: 92%

Section: Resultsmentioning

confidence: 97%

Structure and Reactivity of Polynuclear Divalent Lanthanide Disiloxanediolate Complexes

et al. 2022

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“…The reaction with YbI 3 was carried out at +10 °C and completed within 4 h. Such a distinct behavior of trivalent lanthanides is in good agreement with their typical redox reactions . Divalent samarium could be very easily oxidized assuming a more stable trivalent state, while europium usually retains divalent and takes on the +3 oxidation state only in the presence of strong oxidants. , …”

Section: Resultssupporting

confidence: 66%

Oxidation of [Ge₉{Si(SiMe₃)₃}₃]⁻ with LnI₃ (Ln = Eu, Sm, Yb): Isomerism of Metalloid Germanium Clusters

2022

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The oxidation of K[Ge9(Hyp)3] (Hyp = Si(SiMe3)3) with lanthanide triiodides LnI3 (Ln = Eu, Sm, Yb) leads to the formation of novel clusters with a Ge18-core isolated as a co-crystallizate of Ge*18(Hyp)6 (1a) and Ge18(Hyp)5(Si(SiMe3)2)(SiMe3) (1b). Clusters 1a and 1b differ distinctly from the known cluster Ge18(Hyp)6 (A), which has been found earlier in the reaction of K[Ge9(Hyp)3] with FeCl2 and now identified as an intermediate product in the production of compounds 1a and 1b. These three compounds A, 1a, and 1b are thus structural isomers being the first example of genuine isomerism in metalloid main-group cluster compounds.

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“…The redox-active O,N-coordinated ligand is obviously in a dianionic state, which is confirmed by the single O–C (1.343–1.352 Å) and N–C (1.386–1.404 Å) bonds typical for different o-amidophenolate complexes (1.34–1.36 and 1.38–1.41 Å, respectively) [ 30 , 31 , 32 , 63 , 64 , 65 , 66 , 67 ], as well as by aromatic C–C bonds in six-membered carbon cycles (with the average distances of 1.400, 1.406 and 1.401 Å for 4 – 6 , respectively). The NacNac ligands in 4 – 6 have the same structural features as those in 1 – 3 .…”

Section: Resultsmentioning

confidence: 87%

Low-Coordinate Mixed Ligand NacNac Complexes of Rare Earth Metals

et al. 2023

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We report the synthesis and characterization of two types of new mixed-ligand rare earth complexes: tetracoordinate (NacNacMes)Ln(BIANdipp) (Ln = Dy (1), Er (2) and Y (3)) and pentacoordinate (NacNacMes)Ln(APdipp)(THF) (Ln = Dy (4), Er (5) and Y (6)). The first three compounds were prepared by the reaction of [(BIANDipp)LnI] with potassium β-diketiminate. The salt metathesis of β-diketiminato-supported rare earth dichlorides (NacNacMes)LnCl2(THF)2 with sodium o-amidophenolate results in compounds 4–6. The crystal structures of complexes 1–6 were determined by single-crystal analysis. The combination of bulky monoanionic N-mesityl-substituted β-diketiminates with sterically hindered redox-active ligands led to the very low coordination numbers of rare earths and strong distortion of the chelate ligands.

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Europium and ytterbium complexes with o-iminoquinonato ligands: synthesis, structure, and magnetic behavior

Abstract: Oxidation of Ln(ii) o-amidophenolates with o-iminoquinone leads to ligand mixed-valent o-iminosemiquinonato-o-amidophenolato complexes of Ln(iii).

Cited by 21 publications

References 116 publications

Structure and Reactivity of Polynuclear Divalent Lanthanide Disiloxanediolate Complexes

Structure and Reactivity of Polynuclear Divalent Lanthanide Disiloxanediolate Complexes

Oxidation of [Ge₉{Si(SiMe₃)₃}₃]⁻ with LnI₃ (Ln = Eu, Sm, Yb): Isomerism of Metalloid Germanium Clusters

Low-Coordinate Mixed Ligand NacNac Complexes of Rare Earth Metals

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Europium and ytterbium complexes with o-iminoquinonato ligands: synthesis, structure, and magnetic behavior

Abstract: Oxidation of Ln(ii) o-amidophenolates with o-iminoquinone leads to ligand mixed-valent o-iminosemiquinonato-o-amidophenolato complexes of Ln(iii).

Cited by 21 publications

References 116 publications

Structure and Reactivity of Polynuclear Divalent Lanthanide Disiloxanediolate Complexes

Structure and Reactivity of Polynuclear Divalent Lanthanide Disiloxanediolate Complexes

Oxidation of [Ge9{Si(SiMe3)3}3]− with LnI3 (Ln = Eu, Sm, Yb): Isomerism of Metalloid Germanium Clusters

Low-Coordinate Mixed Ligand NacNac Complexes of Rare Earth Metals

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Oxidation of [Ge₉{Si(SiMe₃)₃}₃]⁻ with LnI₃ (Ln = Eu, Sm, Yb): Isomerism of Metalloid Germanium Clusters