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A Multifunctional Substituted Cyclooctatetraene as a Ligand in Organosamarium Chemistry

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    A Multifunctional Substituted Cyclooctatetraene as a Ligand in Organosamarium Chemistry
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    Institut für Anorganische Chemie, Engesserstrasse Geb. 30.45, D-76128 Karlsruhe, Germany
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    Organometallics

    Cite this: Organometallics 1999, 18, 19, 3835–3842
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    https://doi.org/10.1021/om990259u
    Published August 17, 1999
    Copyright © 1999 American Chemical Society
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    Abstract

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    The reactivity of the multifunctionalized cyclooctatetraene Li2(1,4-R2C8H6) (R = o-(dimethylsilyl)-N,N-dimethylaniline) is reported. To obtain this ligand in large quantities, a new, safe, and convenient method for the preparation of cyclooctatetraene was developed. The ionic complex [Li(diglyme)2][{1,4-R2C8H6}2Sm2(μ-Cl)3] was synthesized by the reaction of the ligand with SmCl3 and characterized by single-crystal X-ray diffraction. The anion of the new complex is an unique example of a dimeric organolanthanide complex which is μ2-bridged by three chlorine atoms. In the solid state the donor functionality does not coordinate to the samarium center. As shown by spin lattice relaxation experiments, there is a coordination of one amino group to the samarium atom in solution. Density functional theory (DFT) calculations show that this coordination might in principle be in an intramolecular fashion. Reaction of Li2(1,4-R2C8H6) with [(C8H8)SmI(THF)2] does not lead to a mixed-sandwich complex. By a ligand rearrangement the nonfunctionalized complex [Li(THF)3{μ-(η2:η8-C8H8)}Sm(C8H8)] was isolated and characterized by single-crystal X-ray diffraction analysis.

    Copyright © 1999 American Chemical Society

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    X-ray experimental details, including tables of positional and anisotropic displacement parameters and bond lengths and angles and additional views of the structures of 2 and 3. This material is available free of charge via the Internet at http://pubs.acs.org.

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    33. Peter W. Roesky. Cyclooctatetraene complexes of yttrium and the lanthanides with chiral and achiral aminotroponiminates. Journal of Organometallic Chemistry 2001, 621 (1-2) , 277-283. https://doi.org/10.1016/S0022-328X(00)00768-3
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    Organometallics

    Cite this: Organometallics 1999, 18, 19, 3835–3842
    Click to copy citationCitation copied!
    https://doi.org/10.1021/om990259u
    Published August 17, 1999
    Copyright © 1999 American Chemical Society
    Request reuse permissions

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