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Issue 11, 2014
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Computational insights into carbon–carbon homocoupling reactions mediated by organolanthanide(III) complexes

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Abstract

Homocoupling of terminal alkynes into trienediyl complexes by alkyl samarocenes is known experimentally. By means of computational techniques, we investigated the mechanism of this reaction in detail. The overall reaction sequence is: σ-bond metathesis, dimerisation of metallocenes, and homocoupling of two acetylides into trienediyl. We show that the rate-determining step corresponds to the homocoupling of two anionic acetylides. This coupling takes place at a bis-samarocene dimer complex in which the bridging mode of the two acetylide moieties is critical for the reaction to proceed. The limited energy barrier for the homocoupling of the carbanions originates from a synergistic effect of the two samarium centres within the dimer. Variation of the steric demand of both substrates and lanthanocenes allowed rationalising all the experimental data available for these systems.

Graphical abstract: Computational insights into carbon–carbon homocoupling reactions mediated by organolanthanide(iii) complexes

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Publication details

The article was received on 17 Oct 2013, accepted on 17 Dec 2013 and first published on 18 Dec 2013


Article type: Paper
DOI: 10.1039/C3DT52937A
Citation: Dalton Trans., 2014,43, 4520-4529
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    Computational insights into carbon–carbon homocoupling reactions mediated by organolanthanide(III) complexes

    C. E. Kefalidis, L. Perrin and L. Maron, Dalton Trans., 2014, 43, 4520
    DOI: 10.1039/C3DT52937A

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