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Diazadienes in lanthanide chemistry: a new insight into old ligands. Synthesis, structures, and properties of complexes {[(R)CNC6H3Pri 2]2}Lu(THF)2(μ-Cl)2Li(THF)2 (R = CH3 or CH2)

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Abstract

The reaction of the dianionic derivative [DADLi2] (DAD is 1,4-bis(2,6-diisopropylphenyl)-2,3-dimethyl-1,4-diazabuta-1,3-diene), which was synthesized in situ by reduction of the corresponding DAD with an excess of metallic lithium in THF, with anhydrous LuCl3 (1: 1) affords the metallacyclic complex {[(Me)CNC6H3Pri 2]2}Lu(THF)2(μ-Cl)2Li(THF)2 (1) containing the enediamide fragment N-C(Me)=C(Me)-N. The treatment of DAD with 2 equiv. of BuLi in a diethyl ether-hexane mixture at 20 °C results in the C-H bond activation of the methyl substituents at the imine carbon atom. The reaction of the in situ formed dilithium derivative [DAD−2HLi2] with LuCl3 in THF afforded the complex {[(CH2)CNC6H3Pri 2]2}-Lu(THF)2(μ-Cl)2Li(THF)2 (2) with the diamide ligand N-C(=CH2)-C(=CH2)-N. The structures of complexes 1 and 2 were established by X-ray diffraction.

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Authors and Affiliations

  1. G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, 49 ul. Tropinina, 603950, Nizhnii Novgorod, Russian Federation

    T. V. Makhrova, G. K. Fukin, A. V. Cherkasov & A. A. Trifonov

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  1. T. V. Makhrova
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  2. G. K. Fukin
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  3. A. V. Cherkasov
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  4. A. A. Trifonov
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Correspondence to A. A. Trifonov.

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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2242–2246, November, 2008.

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Makhrova, T.V., Fukin, G.K., Cherkasov, A.V. et al. Diazadienes in lanthanide chemistry: a new insight into old ligands. Synthesis, structures, and properties of complexes {[(R)CNC6H3Pri 2]2}Lu(THF)2(μ-Cl)2Li(THF)2 (R = CH3 or CH2). Russ Chem Bull 57, 2285–2290 (2008). https://doi.org/10.1007/s11172-008-0322-2

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  • DOI: https://doi.org/10.1007/s11172-008-0322-2

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