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Isolation of (CO)1– and (CO2)1– Radical Complexes of Rare Earths via Ln(NR2)3/K Reduction and [K2(18-crown-6)2]2+ Oligomerization

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    Isolation of (CO)1– and (CO2)1– Radical Complexes of Rare Earths via Ln(NR2)3/K Reduction and [K2(18-crown-6)2]2+ Oligomerization
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    Department of Chemistry, University of California, Irvine, California 92697-2025, United States
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    Cite this: J. Am. Chem. Soc. 2012, 134, 14, 6064–6067
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    https://doi.org/10.1021/ja211220r
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    Deep-blue solutions of Y2+ formed from Y(NR2)3 (R = SiMe3) and excess potassium in the presence of 18-crown-6 at −45 °C under vacuum in diethyl ether react with CO at −78 °C to form colorless crystals of the (CO)1– radical complex, {[(R2N)3Y(μ-CO)2][K2(18-crown-6)2]}n, 1. The polymeric structure contains trigonal bipyramidal [(R2N)3Y(μ-CO)2]2– units with axial (CO)1– ligands linked by [K2(18-crown-6)2]2+ dications. Byproducts such as the ynediolate, [(R2N)3Y]2(μ-OC≡CO){[K(18-crown-6)]2(18-crown-6)}, 2, in which two (CO)1– anions are coupled to form (OC≡CO)2–, and the insertion/rearrangement product, {(R2N)2Y[OC(═CH2)Si(Me2)NSiMe3]}[K(18-crown-6)], 3, are common in these reactions that give variable results depending on the specific reaction conditions. The CO reduction in the presence of THF forms a solvated variant of 2, the ynediolate [(R2N)3Y]2(μ-OC≡CO)[K(18-crown-6)(THF)2]2, 2a. CO2 reacts analogously with Y2+ to form the (CO2)1– radical complex, {[(R2N)3Y(μ-CO2)2][K2(18-crown-6)2]}n, 4, that has a structure similar to that of 1. Analogous (CO)1– and (OC≡CO)2– complexes of lutetium were isolated using Lu(NR2)3/K/18-crown-6: {[(R2N)3Lu(μ-CO)2][K2(18-crown-6)2]}n, 5, [(R2N)3Lu]2(μ-OC≡CO){[K(18-crown-6)]2(18-crown-6)}, 6, and [(R2N)3Lu]2(μ-OC≡CO)[K(18-crown-6)(Et2O)2]2, 6a.

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    Cite this: J. Am. Chem. Soc. 2012, 134, 14, 6064–6067
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ja211220r
    Published March 21, 2012
    Copyright © 2012 American Chemical Society
    Request reuse permissions

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