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Dimeric Rhodium–Ethylene NHC Complexes As Reactive Intermediates for the Preparation of Tetra-heteroleptic NHC Complexes

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    Dimeric Rhodium–Ethylene NHC Complexes As Reactive Intermediates for the Preparation of Tetra-heteroleptic NHC Complexes
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    Department of Chemistry, Queen’s University, Chernoff Hall, 90 Bader Lane, Kingston, Ontario, Canada K7L 3N6
    E-mail: [email protected]
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    Organometallics

    Cite this: Organometallics 2011, 30, 23, 6423–6432
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    https://doi.org/10.1021/om200710y
    Published November 15, 2011
    Copyright © 2011 American Chemical Society
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    Abstract

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    Dimeric rhodium complexes with various N-heterocyclic carbene (NHC) ligands have been synthesized and fully characterized. X-ray analysis unambiguously confirms the bimetallic nature of these complexes, and in all cases one molecule of ethylene is coordinated to each metal center in an η2-fashion. The Rh atoms are also coordinated to one NHC ligand and are interconnected by two μ-chlorine bridges. The dimeric nature of the complexes is most likely stabilized due to the significant steric bulk around the metal centers provided by the carbene ligands. Consistent with this, modulating the steric properties and backbone saturation of the ligands was shown to have a significant effect on the stability and geometry of the complexes. Treatment of the carbene dimers with ligands such as PPh3 results in cleavage of the dimers and a unique synthesis of tetra-heteroleptic complexes of the general formula [ClRh(NHC)(PR3)(CH2═CH2)]. The stabilities of these compounds have been assessed, and although decomposition to Wilkinson’s complex is observed upon treatment with an excess of phosphine for prolonged times, the presence of the ethylene ligand provides greatly increased stability compared with the bis-phosphine analogues [ClRh(NHC)(PPh3)2].

    Copyright © 2011 American Chemical Society

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    Cited By

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    Organometallics

    Cite this: Organometallics 2011, 30, 23, 6423–6432
    Click to copy citationCitation copied!
    https://doi.org/10.1021/om200710y
    Published November 15, 2011
    Copyright © 2011 American Chemical Society
    Request reuse permissions

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