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  • 1
    ISSN: 0044-2313
    Keywords: Yttrium(III) ; samarium(II) ; benzyl complexes ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Lanthanide Halides with Alkalibenzyl Compounds. Synthesis and Crystal Structures of [(tmeda)(C6H5CH2)2Y(μ-Br)2Li(tmeda)], [(tmeda)2SmBr(μ-Br)2Li(tmeda)] and [(dme)2SmBr(μ-Br)]2Alkali-benzyl compounds react via a metathesis reaction with lanthanide halides to benzyl complexes of the rare earths. Reaction of [(C6H5CH2)Li(tmeda)] with YBr3 leads to the complex [(tmeda)Y(C6H5CH2)2 (μ-Br)2Li(tmeda)] 1, in which Yttrium and lithium are linked via two bromide bridges. However, the reaction of [(C6H5CH2)Li(tmeda)] with SmBr3 in toluene/tmeda leads under reduction of the Sm ion to the compound [(tmeda)2SmBr(μ-Br)2Li(tmeda)] 2. 2 reacts with DME to yield the dimeric compound [(dme)2SmBr(μ-Br)]2 3. The structures of 1-3 were determined by X-ray single crystal structure analysis:1:Space group P21/c, Z = 4, a = 829.5(6) pm, b = 1477.9(11) pm, c = 2575.0(10) pm, β = 92.03(6)°,2:Space group P21, Z = 2, a = 954,7(3) pm, b = 1338.5(6) pm, c = 1244.9(5) pm, β = 107.51(3)°,3:Space group P1, Z = 1, a = 797.2(7) pm, b = 818.3(7) pm, c = 1169.7(8) pm, α = 100.96(6)°, β = 92.03(6)°, γ = 91.75(7)°.
    Notes: Alkalibenzylverbindungen reagieren mit Lanthanoidhalogeniden unter Salzabspaltung zu Benzylkomplexen der Seltenen Erden. [(C6H5CH2)Li(tmeda)] bildet mit YBr3 den Komplex [(tmeda)(C6H5CH2)2Y(μ-Br)2Li(tmeda)] 1, in dem das Yttriumion mit Lithium über zwei Bromo-Brücken verknüpft ist. Bei der Reaktion von [(C6H5CH2)Li(tmeda)] mit SmBr3 in Toluol/TMEDA erfolgt hingegen unter Reduktion die Bildung von [(tmeda)2SmBr(μ-Br)2Li(tmeda)] 2. Diese Verbindung bildet mit DME den zweikernigen Komplex [(dme)2SmBr(μ-Br)]2 3. Die Strukturen von 1, 2 und 3 wurden durch Einkristallstrukturanalyse geklärt:1:Raumgruppe P21/c, Z = 4, a = 829,5(6) pm, b = 1477,9(11) pm, c = 2575,0(10) pm, β = 92,03(6)°,2:Raumgruppe P21, Z = 2, a = 954,7(3) pm, b = 1338,5(6) pm, c = 1244,9(5) pm, β = 107,51(3)°,3:Raumgruppe P1, Z = 1, a = 797,2(7) pm, b = 818,3(7) pm, c = 1169,7(8) pm, α = 100,96(6)°, β = 92,03(6)°, γ = 91,75(7)°.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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