Faculté des sciences

Analogy of the Coordination Chemistry of Alkaline Earth Metal and Lanthanide Ln²⁺ Ions: The Isostructural Zoo of Mixed Metal Cages [IM(OtBu)₄{Li(thf)}₄(OH)] (M=Ca, Sr, Ba, Eu), [MM′₆(OPh)₈(thf)₆] (M=Ca, Sr, Ba, Sm, Eu, M′=Li, Na), and their Derivatives with 1,2-Dimethoxyethane

Maudez, William ; Meuwly, Markus ; Fromm, Katharina M.

In: Chemistry - A European Journal, 2007, vol. 13, no. 29, p. 8302 - 8316

As previously shown, alkali and alkaline earth metal iodides in nonaqueous, aprotic solvents behave like transition metal halides, forming cis- and trans-dihalides with various neutral O-donor ligands. These compounds can be used as precursors for the synthesis of new mixed alkali/alkaline earth metal aggregates. We show here that Ln²⁺ ions form isostructural cluster compounds.... Plus

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    Summary
    As previously shown, alkali and alkaline earth metal iodides in nonaqueous, aprotic solvents behave like transition metal halides, forming cis- and trans-dihalides with various neutral O-donor ligands. These compounds can be used as precursors for the synthesis of new mixed alkali/alkaline earth metal aggregates. We show here that Ln²⁺ ions form isostructural cluster compounds. Thus, with LiOtBu, 50 % of the initial iodide can be replaced in MI₂, M=Ca, Sr, Ba, Eu, to generate the mixed-metal alkoxide aggregates [IM(OtBu)₄{Li(thf)}₄(OH)], for which the M***Missing image substitution***OH contacts were investigated by theoretical methods. With M′OPh (M′=Li, Na), a new mixed-metal aryloxide cluster type [MM′₆(OPh)₈(thf)₆] is obtained for M=Ca, Sr, Ba, Sm, Eu. Their stability versus DME (DME=1,2-dimethoxyethane) as bidentate ligand is studied.