Synthesis and structure of a heterotrimetallic (Li/Er/In), heptacyclic metallasiloxane cage compound

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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Synthesis and structure of a heterotrimetallic (Li/Er/In), heptacyclic metallasiloxane cage compound

Cited by 6 publications

References 29 publications

Synthesis and Structural Characterization of Homo‐ and Heterometallic Li and Li/Ln Disiloxanediolate Complexes

Synthesis and Structural Characterization of Homo‐ and Heterometallic Li and Li/Ln Disiloxanediolate Complexes

Modern concepts and methods in the chemistry of polyhedral metallasiloxanes

Structure and Reactivity of Polynuclear Divalent Lanthanide Disiloxanediolate Complexes

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