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From NHC to Imidazolyl Ligand: Synthesis of Platinum and Palladium Complexes d10-[M(NHC)2] (M = Pd, Pt) of the NHC 1,3-Diisopropylimidazolin-2-ylidene

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    From NHC to Imidazolyl Ligand: Synthesis of Platinum and Palladium Complexes d10-[M(NHC)2] (M = Pd, Pt) of the NHC 1,3-Diisopropylimidazolin-2-ylidene
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    Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, D-97074 Würzburg, Germany
    *E-mail: [email protected]
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    Organometallics

    Cite this: Organometallics 2015, 34, 13, 3236–3245
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    https://doi.org/10.1021/acs.organomet.5b00277
    Published June 23, 2015
    Copyright © 2015 American Chemical Society
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    Abstract

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    The widely held belief that N-heterocyclic carbenes (NHCs) act only as innocent spectator ligands is not always accurate, even in the context of well-explored reactions. Ligand exchange in the conversion of [Pt(PPh3)2(η2-C2H4)] (3) to [Pt(iPr2Im)2] (2) depends critically on the particular reaction conditions employed, with slight changes leading to vastly different outcomes. In addition to [Pt(iPr2Im)2] (2), complexes [Pt(iPr2Im)(PPh3)(η2-C2H4)] (5) and trans-[Pt(iPr2Im)2(iPr-Im*)(H)] (6) were isolated and in the case of 6 fully characterized. Complex 5 represents the first mixed-olefin complex in transition metal chemistry containing both an NHC and a phosphine ligand. Chemical degradation of the NHC was shown to yield the new imidazole-2-yl iPr-Im* in 6. Therefore, the synthesis of [Pt(iPr2Im)2] (2) via metallic reduction of the ionic precursor [Pt(iPr2Im)3(Cl)]+Cl– (9) is favorable, a procedure adaptable to analogous palladium compounds. While [Pd(iPr2Im)3(Cl)]+Cl– (8) is the only product obtained from the reaction of iPr2Im and PdCl2, neutral [Pt(iPr2Im)2(Cl)2] (10), formed as a mixture of its two stereoisomers cis-10 and trans-10, is available through precise control of the stoichiometry in the reaction of PtCl2 and exactly 2 equiv of iPr2Im.

    Copyright © 2015 American Chemical Society

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    Figures, tables, spectra, and CIF and XYZ files giving experimental and computational details. Crystallographic data, DFT-optimized energies, and coordinates. The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.organomet.5b00277.

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    Cited By

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    This article is cited by 29 publications.

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    Organometallics

    Cite this: Organometallics 2015, 34, 13, 3236–3245
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.organomet.5b00277
    Published June 23, 2015
    Copyright © 2015 American Chemical Society
    Request reuse permissions

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